Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels and foams

ABSTRACT

A polymer film, polymer gel, and polymer foam each contain an electrically conductive polymer and an ionic liquid and are each useful as a component of an electronic device.

FIELD OF THE INVENTION

The present invention relates to polymer compositions, films, gels, andfoams, more particularly polymer compositions, films, gels, and foamscomprising electrically conductive polymers, and electronic devicescontaining such polymer films, gels, and foams.

BACKGROUND

Transparent conductors, such as Indium Tin Oxide (ITO), combine theelectrical conductivity of metal with the optical transparency of glassand are useful as components in electronic devices, such as in displaydevices. Flexibility is likely to become a broader challenge for ITO,which does not seem well suited to the next generation of display,lighting, or photovoltaic devices. These concerns have motivated asearch for replacements using conventional materials and nanomaterials.There is variety of technical approaches for developing ITO substitutesand there are four areas in which these various alternatives compete:price, electrical conductivity, optical transparency, and physicalresiliency.

Electrically conductive polymers, such as polythiophene polymers,particularly a polymer blend of poly(3,4-ethylenedioxythiophene) andpoly(styrene sulfonate) (“PEDOT-PSS”) have been investigated as possiblealternatives to ITO. The electrical conductivity of electricallyconductive polymers is typically lower than that of ITO, but can beenhanced through the use of conductive fillers, such as carbonnanotubes, and dopants. However, the performance of such films stillfalls short of that of ITO and trade-offs exist between optimizing theelectrical conductivity and optimizing the optical transparency ofelectrically conductive polymers films.

There has been some interest in modifying the properties of electricallyconductive polymer films using ionic liquids. U.S. Pat. No. 842,197,issued Nov. 30, 2010, broadly discloses mixtures of electricallyconductive polymers and ionic liquids, including specifically, mixturesof PEDOT-PSS and 1-butyl-3-methyl-imidazolium tetrafluoroborate. U.S.Pat. No. 7,842,197, issued Nov. 30, 2010, discloses a method forproducing a conductive material by contacting an electrically conductivepolymer with certain ionic liquids U.S. Patent Application Publication2008/0139710 A1, published Jun. 12, 2008, discloses conductive gelscomprising certain conductive polymers dispersed or dissolved in certainionic liquids, in combination with certain gelling agents.

There is an ongoing unresolved interest in increasing the electricalconductivity and optical transparency of electrically conductive polymerfilms, more specifically of PEDOT-PSS films.

SUMMARY OF THE INVENTION

In a first aspect, the present invention is directed to a polymer film,comprising a mixture of:

(a) an electrically conductive polymer, and

(b) an ionic liquid.

In one embodiment, the polymer film comprises:

-   (a) one or more electrically conductive polymers selected from    polythiophene polymers, polyselenophene polymers, polytelurophene    polymers, polypyrrole polymers, polyaniline polymers, fused    heterocyclic heteroaromatic polymers and mixtures thereof, and,    optionally, further comprising one or more water soluble polymeric    acid dopants, and-   (b) an ionic liquid, comprising one or more compounds each    comprising:    -   (i) an organic cation, and    -   (ii) an anion selected from cyanate anions, tetracyanoborate        anions, tetrakis-(p-(dimethyl(1H, 1H, 2H,        2H-per-fluorooctyl)silyl)phenyl)borate anions, and        hexafluorophosphate anions,        provided that, if the ionic liquid comprises a compound that        comprises a hexafluorophosphate anion, then the one or more        electrically conductive polymers must comprise a mixture of one        or more polythiophene polymers and one or more water soluble        polymeric acid dopants.

In a second aspect, the present invention is directed to a method formaking a polymer film according to the present invention, comprising:

-   (A) forming a layer of a polymer composition, said polymer    composition comprising    -   (a) a liquid carrier,    -   (b) one or more electrically conductive polymers dissolved or        dispersed in the liquid carrier, and    -   (c) one or more ionic liquids dissolved or dispersed in the        liquid carrier, and-   (B) removing the liquid carrier from the layer.

In a third aspect, the present invention is directed to a polymercomposition useful in making a polymer film according to the presentinvention, and comprising:

(a) a liquid carrier,

(b) an electrically conductive polymer dissolved or dispersed in theliquid carrier, and

(c) an ionic liquid dissolved or dispersed in the liquid carrier.

In a fourth aspect, the present invention is directed to a method formaking a polymer composition comprising providing a solution ordispersion of an electrically conductive polymer in a liquid carrier anddissolving or dispersing an ionic liquid in the solution or dispersionof the electrically conductive polymer in the liquid carrier.

In a fifth aspect, the present invention is directed to an electronicdevice, comprising a plurality of layers, wherein at least one layer ofthe plurality of layers comprises polymer film according to the presentinvention.

The respective polymer film of the present invention and polymer filmcomponent of the electronic device of the present invention eachtypically provide high electrical conductivity, as well as, in someembodiments, high optical transmittance. In one embodiment, the polymerfilm of the present invention exhibits a sheet resistance of less thanor equal to about 500 Ohms per square. In one embodiment, polymer filmof the present invention exhibits a conductivity of greater than 500Siemens per centimeter.

In a sixth aspect, the present invention is directed to an electricallyconductive polymer gel, comprising the gelled combination of anelectrically conductive polymer, an ionic liquid, and an aqueous liquidmedium.

In one embodiment, the polymer gel comprises:

(a) a polymer network, comprising:

-   -   (i) an electrically conductive polymer, comprising:        -   (1) one or more electrically conductive polythiophene            polymers, and        -   (2) one or more water soluble polymeric acid dopants, and    -   (ii) an amount of one or more ionic liquids effective to gel the        electrically conductive polymer, and        (b) a liquid medium supported within the polymer network.

In a seventh aspect, the present invention is directed to a method formaking an electrically conductive polymer gel, comprising contacting, inan aqueous liquid medium, one or more electrically conductive polymersand an amount of one or more ionic liquids effective to gel the one ormore electrically conductive polymers.

In an eighth aspect, the present invention is directed to an electronicdevice, comprising a plurality of layers, wherein at least one layer ofthe plurality of layers comprises a polymer gel according to the presentinvention.

In a ninth aspect, the present invention is directed to a polymer foam,comprising a porous polymer network of the combination of anelectrically conductive polymer and an ionic liquid.

In one embodiment, the polymer foam comprises a porous network, saidporous network comprising the product obtained by:

(a) contacting, in a liquid medium:

-   -   (i) an electrically conductive polymer, comprising:        -   (1) one or more electrically conductive polythiophene            polymers, and        -   (2) one or more water soluble polymeric acid dopants, and    -   (ii) an amount of one or more ionic liquids effective to gel the        electrically conductive polymer, and        (b) removing the liquid medium from the gel.

In a tenth aspect, the present invention is directed to a method formaking an electrically conductive polymer foam, comprising

-   -   (A) contacting in a liquid medium, typically an aqueous liquid        medium, one or more electrically conductive polymers and an        amount of one or more ionic liquids effective to gel the one or        more electrically conductive polymers to form a polymer gel, and    -   (B) removing the liquid medium from the polymer gel.

In an eleventh aspect, the present invention is directed to, the presentinvention is directed to an electronic device, comprising a plurality oflayers, wherein at least one layer of the plurality of layers comprisesa polymer foam according to present invention.

In one embodiment, the polymer foam exhibits a sheet resistance of lessthan or equal to about 50 Ohms per square.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an electronic device according to thepresent invention.

FIG. 2 is a plot of Conductivity, expressed in Siemens per centimeter(“S cm⁻¹”) versus amount of ionic liquid in the film, expressed aspercent by weight of the film (“wt %”), for thepoly(3,4-ethylenedioxythiophene):poly(styrene sulfonicacid)/1-ethyl-3-methylimidazolium tetracyanoborate films of Examples 35to 38, as described below (“PEDOT PSS EMIM TCB P1”), and Examples 39 to43, as described below (“PEDOT PSS EMIM TCB P2”), and of thepoly(3,4-ethylenedioxythiophene):poly(styrene sulfonicacid)/1-ethyl-3-methylimidazolium tetrafluoroborate films of ComparativeExamples C32 to C36, as described below ((“PEDOT PSS EMIM BF4 P2”).

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the following terms have the meanings ascribed below:

“acidic group” means a group capable of ionizing to donate a hydrogenion,

“anode” means an electrode that is more efficient for injecting holescompared to than a given cathode,

“buffer layer” generically refers to electrically conductive orsemiconductive materials or structures that have one or more functionsin an electronic device, including but not limited to, planarization ofan adjacent structure in the device, such as an underlying layer, chargetransport and/or charge injection properties, scavenging of impuritiessuch as oxygen or metal ions, and other aspects to facilitate or toimprove the performance of the electronic device,

“cathode” means an electrode that is particularly efficient forinjecting electrons or negative charge carriers,

“confinement layer” means a layer that discourages or prevents quenchingreactions at layer interfaces,

“doped” as used herein in reference to an electrically conductivepolymer means that the electrically conductive polymer has been combinedwith a polymer counterion for the electrically conductive polymer, whichpolymer counterion is referred to herein as “dopant”, and is typically apolymer acid, which is referred to herein as a “polymer acid dopant”,

“doped electrically conductive polymer” means a polymer blend comprisingan electrically conductive polymer and a polymer counterion for theelectrically conductive polymer,

“electrically conductive polymer” means any polymer or polymer blendthat is inherently or intrinsically, without the addition ofelectrically conductive fillers such as carbon black or conductive metalparticles, capable of electrical conductivity, more typically to anypolymer or oligomer that exhibits a bulk specific conductance of greaterthan or equal to 10⁻⁷ Siemens per centimeter (“S/cm”), unless otherwiseindicated, a reference herein to an “electrically conductive polymer”include any optional polymer acid dopant,

“electrically conductive” includes conductive and semi-conductive,

“electroactive” when used herein in reference to a material orstructure, means that the material or structure exhibits electronic orelectro-radiative properties, such as emitting radiation or exhibiting achange in concentration of electron-hole pairs when receiving radiation,

“electronic device” means a device that comprises one or more layerscomprising one or more semiconductor materials and makes use of thecontrolled motion of electrons through the one or more layers,

“electron injection/transport”, as used herein in reference to amaterial or structure, means that such material or structure thatpromotes or facilitates migration of negative charges through suchmaterial or structure into another material or structure,

“high-boiling solvent” refers to an organic compound which is a liquidat room temperature and has a boiling point of greater than 100° C.,

“hole transport” when used herein when referring to a material orstructure, means such material or structure facilitates migration ofpositive charges through the thickness of such material or structurewith relative efficiency and small loss of charge,

“layer” as used herein in reference to an electronic device, means acoating covering a desired area of the device, wherein the area is notlimited by size, that is, the area covered by the layer can, forexample, be as large as an entire device, be as large as a specificfunctional area of the device, such as the actual visual display, or beas small as a single sub-pixel,

“polymer” includes homopolymers and copolymers,

“polymer blend” means a blend of two or more polymers, and

“polymer network” means a three dimensional structure of interconnectedsegments of one or more polymer molecules, in which the segments are ofa single polymer molecule and are interconnected by covalent bonds (a“crosslinked polymer network”), in which the segments are of two or morepolymer molecules and are interconnected by means other than covalentbonds, (such as physical entanglements, hydrogen bonds, or ionic bonds)or by both covalent bonds and by means other than covalent bonds (a“physical polymer network”).

As used herein, the terminology “(C_(x)-C_(y))” in reference to anorganic group, wherein x and y are each integers, means that the groupmay contain from x carbon atoms to y carbon atoms per group.

As used herein, the term “alkyl” means a monovalent straight, branchedor cyclic saturated hydrocarbon radical, more typically, a monovalentstraight or branched saturated (C₁-C₄₀)hydrocarbon radical, such as, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, hexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl,tricontyl, and tertacontyl. As used herein, the term “cycloalkyl” meansa saturated hydrocarbon radical, more typically a saturated (C₅-C₂₂)hydrocarbon radical, that includes one or more cyclic alkyl rings, whichmay optionally be substituted on one or more carbon atoms of the ringwith one or two (C₁-C₆)alkyl groups per carbon atom, such as, forexample, cyclopentyl, cycloheptyl, cyclooctyl. The term “heteroalkyl”means an alkyl group wherein one or more of the carbon atoms within thealkyl group has been replaced by a hetero atom, such as nitrogen,oxygen, sulfur. The term “alkylene” refers to a divalent alkyl groupincluding, for example, methylene, and poly(methylene).

As used herein, the term “hydroxyalkyl” means an alkyl radical, moretypically a (C₁-C₂₂)alkyl radical, that is substituted with one or morehydroxyl groups, including, for example, hydroxymethyl, hydroxyethyl,hydroxypropyl, and hydroxydecyl.

As used herein, the term “alkoxyalkyl” means an alkyl radical that issubstituted with one or more alkoxy substituents, more typically a(C₁-C₂₂)alkyloxy-(C₁-C₆)alkyl radical, including, for example,methoxymethyl, and ethoxybutyl.

As used herein, the term “alkenyl” means an unsaturated straight orbranched hydrocarbon radical, more typically an unsaturated straight,branched, (C₂-C₂₂) hydrocarbon radical, that contains one or morecarbon-carbon double bonds, including, for example, ethenyl, n-propenyl,and iso-propenyl,

As used herein, the term “cycloalkenyl” means an unsaturated hydrocarbonradical, typically an unsaturated (C₅-C₂₂) hydrocarbon radical, thatcontains one or more cyclic alkenyl rings and which may optionally besubstituted on one or more carbon atoms of the ring with one or two(C₁-C₆)alkyl groups per carbon atom, including, for example,cyclohexenyl and cycloheptenyl.

As used herein, the term “aryl” means a monovalent unsaturatedhydrocarbon radical containing one or more six-membered carbon rings inwhich the unsaturation may be represented by three conjugated doublebonds, which may be substituted one or more of carbons of the ring withhydroxy, alkyl, alkoxyl, alkenyl, halo, haloalkyl, monocyclic aryl, oramino, including, for example, phenyl, methylphenyl, methoxyphenyl,dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl,triisobutyl phenyl, tristyrylphenyl, and aminophenyl.

As used herein, the term “aralkyl” means an alkyl group substituted withone or more aryl groups, more typically a (C₁-C₁₈)alkyl substituted withone or more (C₆-C₁₄)aryl substituents, including, for example,phenylmethyl, phenylethyl, and triphenylmethyl.

As used herein, the term “polycyclic heteroaromatic” refers to compoundshaving more than one aromatic ring, at least one of which includes atleast one hetero atom in the ring, wherein adjacent rings may be linkedto each other by one or more bonds or divalent bridging groups or may befused together.

As used herein, the following terms refer to the correspondingsubstituent groups:

“amido” is —R¹—C(O)N(R⁶)R⁶,

“amidosulfonate” is —R¹—C(O)N(R⁴)R²—SO₃Z,

“benzyl” is —CH₂—C₆H₅,

“carboxylate” is —R¹—C(O)O—Z or —R¹—O—C(O)—Z,

“ether” is —R¹—(O—R³)_(p)—O—R³,

“ether carboxylate” is —R¹—O—R²—C(O)O—Z or —R¹—O—R²—O—C(O)—Z,

“ether sulfonate” is —R¹—O—R²—SO₃Z,

“ester sulfonate” is —R¹—O—C(O)R²—SO₃Z,

“sulfonimide” is —R¹—SO₂—NH—SO₂—R³, and

“urethane” is —R¹—O—C(O)—N(R⁴)₂,

wherein:

each R¹ is absent or alkylene,

each R² is alkylene,

each R³ is alkyl,

each R⁴ is H or an alkyl,

p is 0 or an integer from 1 to 20, and

each Z is H, alkali metal, alkaline earth metal, N(R³)₄ or R³,

wherein any of the above groups may be non-substituted or substituted,and any group may have fluorine substituted for one or more hydrogens,including perfluorinated groups.

In one embodiment, respective polymer film of the present invention andpolymer film component of the electronic device of the present inventioneach comprise, based on 100 parts by weight (“pbw”) of the polymer film:

-   (i) from about 1 to about 99.9 pbw, more typically from about 2 to    about 99.9 pbw, and even more typically from about 10 to about 80    pbw of the electrically conductive polymer, and-   (ii) from about 0.1 to about 99 pbw, more typically from about 0.1    to about 97.5 pbw, and even more typically from about 20 to about 90    pbw of the ionic liquid.

In one embodiment, the electrically conductive polymer of the respectivepolymer film of the present invention and/or polymer film component ofthe electronic device of the present invention forms a continuous phaseand the ionic liquid forms a discontinuous phase that is dispersed inthe continuous electrically conductive polymer phase.

In one embodiment, the electrically conductive polymer of the respectivepolymer film of the present invention and/or polymer film component ofthe electronic device of the present invention forms a polymer networkand polymer network is impregnated with the ionic liquid.

In one embodiment, the electrically conductive polymer of the respectivepolymer film of the present invention and/or polymer film component ofthe electronic device of the present invention, forms a physical polymernetwork of non-crosslinked molecules of the electrically conductivepolymer.

In one embodiment, the electrically conductive polymer of the respectivepolymer film of the present invention and/or polymer film component ofthe electronic device of the present invention forms a crosslinkedpolymer network.

In one embodiment, the respective polymer film of the present inventionand polymer film component of the electronic device of the presentinvention each comprise, based on 100 pbw of the polymer film:

-   (i) from greater than 25 pbw to about 99.9 pbw, more typically from    greater than 25 pbw to about 99.9 pbw, and even more typically from    greater than 25 pbw to about 80 pbw of the electrically conductive    polymer, and-   (ii) from about 0.1 to less than 75 pbw, more typically from about    0.1 to less than 75 pbw, and even more typically from about 20 to    less than 75 pbw of the ionic liquid.

In one embodiment of the respective polymer film of the presentinvention and polymer film component of the electronic device of thepresent invention, the ratio of the total amount by weight of the ionicliquid in such film to the total amount by weight of the electricallyconductive polymer in such film is typically from greater than 0:1 toabout 1.5:1, more typically from about 0.1:1 to 1:1.

In one embodiment, the respective polymer film of the present inventionand polymer film component of the electronic device of the presentinvention each comprise, based on 100 pbw of the polymer film:

-   (i) from greater than 25 pbw to about 99.9 pbw, more typically from    greater than 25 pbw to about 99.9 pbw, and even more typically from    greater than 25 pbw to about 80 pbw of the electrically conductive    polymer, and-   (ii) from about 0.1 to less than 75 pbw, more typically from about    0.1 to less than 75 pbw, and even more typically from about 20 to    less than 75 pbw of the ionic liquid, and    the ratio of the total amount by weight of the ionic liquid in such    film to the total amount by weight of the electrically conductive    polymer in such film is typically from greater than 0:1 to about    1.5:1, more typically from about 0.1:1 to 1:1.

In one embodiment, respective polymer film of the present invention andpolymer film component of the electronic device of the present inventioneach comprise a discontinuous ionic liquid phase dispersed within acontinuous phase of the electrically conductive polymer, and typicallyexhibit good chemical stability, low flammability, negligible vaporpressure, and high ionic conductivity.

In one embodiment, the polymer gel of the present invention comprises,based on 100 pbw of the gel,

(a) from about 2 pbw to about 90 pbw of a polymer network, said networkcomprising, based on 100 pbw of said network:

-   -   (i) from about 10 to about 40 pbw, more typically from about 15        to about 35 pbw, and even more typically from about 20 to about        35 pbw of the electrically conductive polymer, and    -   (ii) from about 60 to about 90 pbw, more typically from about 65        to about 85 pbw, and even more typically from about 65 to about        80 pbw of the ionic liquid, and        (b) from about 10 pbw to about 98 pbw of an aqueous liquid        medium.

In one embodiment of the polymer gel of the present invention, the ratioof the total amount by weight of the ionic liquid in such gel to thetotal amount by weight of the electrically conductive polymer in suchgel is typically from about 1.5:1 to about 45:1, more typically from1.7:1 to 20:1, even more typically from about 1.7:1 to about 10:1, andstill more typically from 2:1 to 8:1.

In one embodiment, the polymer gel of the present invention comprises,based on 100 pbw of the gel,

(a) from about 2 pbw to about 90 pbw of a polymer network, said networkcomprising, based on 100 pbw of said network:

-   -   (i) from about 10 to about 40 pbw, more typically from about 15        to about 35 pbw, and even more typically from about 20 to about        35 pbw of the electrically conductive polymer, and    -   (ii) from about 60 to about 90 pbw, more typically from about 65        to about 85 pbw, and even more typically from about 65 to about        80 pbw of the ionic liquid, and        (b) from about 10 pbw to about 98 pbw of an aqueous liquid        medium, and the ratio of the total amount by weight of the ionic        liquid in such gel to the total amount by weight of the        electrically conductive polymer in such gel is typically from        about 1.5:1 to about 45:1, more typically from 1.7:1 to 20:1,        even more typically from about 1.7:1 to about 10:1, and still        more typically from 2:1 to 8:1.

In one embodiment, the polymer network of the polymer gel of the presentinvention comprises a reaction product of the electrically conductivepolymer and the ionic liquid. In one embodiment, the polymer network isimpregnated with the aqueous liquid medium. In one embodiment, thestorage modulus, G′, of the polymer gel exceeds the loss modulus, G″, ofthe polymer gel at any angular frequency within a range of from about0.01 to about 100 radians/second, as determined by dynamic oscillatorymeasurements using a dynamic mechanical analysis instrument, such as,for example, a TA Instruments Q400 DMA.

In one embodiment, the polymer foam of the present invention and polymerfoam component of the electronic device of the present invention eachcomprise the product obtained by contacting, typically in a liquidmedium, based on 100 pbw of the polymer foam:

-   (i) from about 10 to about 40 pbw, more typically from about 15 to    about 35 pbw, and even more typically from about 20 to about 35 pbw    of the electrically conductive polymer, and-   (ii) from about 60 to about 90 pbw, more typically from about 65 to    about 85 pbw, and even more typically from about 65 to about 80 pbw    of the ionic liquid,

In one embodiment of the polymer foam of the present invention andpolymer foam component of the electronic device of the presentinvention, the ratio of the total amount by weight of the ionic liquidin such foam to the total amount by weight of the electricallyconductive polymer in such foam is typically from about 1.5:1 to about45:1, more typically from 1.7:1 to 20:1, even more typically from about1.7:1 to about 10:1, and still more typically from 2:1 to 8:1.

In one embodiment, the polymer foam of the present invention and polymerfoam component of the electronic device of the present invention eachcomprise the product obtained by contacting, based on 100 pbw of thepolymer foam:

-   (i) from about 10 to about 40 pbw, more typically from about 15 to    about 35 pbw, and even more typically from about 20 to about 35 pbw    of the electrically conductive polymer, and-   (ii) from about 60 to about 90 pbw, more typically from about 65 to    about 85 pbw, and even more typically from about 65 to about 80 pbw    of the ionic liquid, and    the ratio of the total amount by weight of the ionic liquid in such    foam to the total amount by weight of the electrically conductive    polymer in such foam is typically from about 1.5:1 to about 45:1,    more typically from 1.7:1 to 20:1, even more typically from about    1.7:1 to about 10:1, and still more typically from 2:1 to 8:1.

In one embodiment, the polymer foam of the present invention comprises areaction product of the electrically conductive polymer and the ionicliquid. In one embodiment, the polymer foam has a porous structure, ahigh strength to weight and surface area to volume ratios, and highelectrical conductivity. In one embodiment, the storage modulus, G′, ofthe polymer foam exceeds the loss modulus, G″, of the polymer foam atany angular frequency within a range of from about 0.01 to about 100radians/second, as determined by dynamic oscillatory measurements usinga dynamic mechanical analysis instrument, such as, for example, a TAInstruments Q400 DMA.

In one embodiment, the polymer composition of the present inventioncomprises, based on 100 pbw of the polymer composition:

-   (a) from greater than 0 to less than 100 pbw, more typically from    about 50 to less than 100 pbw, even more typically from about 90 to    about 99.5 pbw of liquid carrier,-   (b) from greater than 0 to less than 100 pbw, more typically from    greater than 0 to about 50 pbw, even more typically from 0.5 to    about 10 pbw, of the mixture of electrically conductive polymer and    ionic liquid, comprising, based on 100 pbw of the total amount of    the electrically conductive polymer and the ionic liquid;    -   (i) from about 1 to about 99.9 pbw, more typically from about 2        to about 99.9 pbw, and even more typically from about 25 to        about 80 pbw of the electrically conductive polymer, and    -   (ii) from about 0.1 to about 99 pbw, more typically from about        0.1 to about 97.5 pbw, and even more typically from about 20 to        about 75 pbw of the ionic liquid.

As mentioned above, U.S. Patent Application Publication 2008/0139710 A1,published Jun. 12, 2008, discloses conductive gels comprising certainconductive polymers dispersed or dissolved in certain ionic liquids, incombination with certain gelling agents. Suitable gelling agents aresaid to include compounds having at least two polar groups, such aspentaerythritol, or compounds that have at least two reactive functionalgroups, such as isocyanate compounds having at least two isocyanategroups, wherein an intermolecular bond, such as a hydrogen bond, isformed between the polar groups of the gelling agent or a covalent bondis formed between the reactive functional of the gelling agent tothereby form a three dimensional network that facilitates gelatin ofsuch composition. While not wishing to be bound by theory, it isbelieved that polymer gel and polymer foam of the present invention eachcomprise the combination of a porous polymer network and aqueous liquidwithin the interstices of the network, that the polymer foam of thepresent invention comprises the porous polymer network that remainsafter removal of some or all of the liquid medium component of thepolymer gel of the present invention, and that in each case, the porouspolymer network is a product of an association or a reaction between theelectrically conductive polymer and the ionic liquid to form a newcompound or complex, in the absence of a separate gelling agent. In anycase, the only components required to form the polymer gel and foamcompositions of the present invention are the liquid carrier, theconductive polymer and the ionic liquid and the polymer gel and polymerfoam of the present invention can thus be and typically are formed inthe absence of a gelling agent. In one embodiment, the polymer gel ofthe present invention does not comprise a gelling agent. In oneembodiment, the polymer foam of the present invention does not comprisea gelling agent.

In one embodiment, the polymer composition of the present invention is apolymer dispersion, wherein the liquid carrier component of thedispersion may be any liquid in which the electrically conductivepolymer component of the composition is insoluble, but within which theelectrically conductive polymer component of the composition isdispersible. In one embodiment, the liquid carrier of the polymercomposition of the present invention is an aqueous medium that compriseswater. In one embodiment, the liquid carrier is an aqueous medium thatconsists essentially of water. In one embodiment, the liquid carrier isan aqueous medium that consists of water. In one embodiment, the liquidcarrier of the polymer composition of the present invention is anon-aqueous medium that comprises one or more water miscible organicliquids. In one embodiment, the liquid carrier of the polymercomposition of the present invention is an aqueous medium that compriseswater and, optionally, one or more water miscible organic liquids, andthe electrically conductive polymer is dispersible in the aqueousmedium. Suitable water miscible organic liquids include polar aproticorganic solvents, such as, for example methanol, ethanol, and propanol.In one embodiment, the liquid carrier comprises, based on 100 pbw of theliquid medium, from about 10 to 100 pbw, more typically from about 50pbw to 100 pbw, and even more typically, from about 90 to 100 pbw, waterand from 0 pbw to about 90 pbw, more typically from 0 pbw to about 50pbw, and even more typically from 0 pbw to about 10 pbw of one or morewater miscible organic liquids.

In one embodiment, the polymer composition is a polymer solution,wherein the liquid carrier component of the composition may be anyliquid in which the electrically conductive polymer component of thecomposition is soluble. In one embodiment, the liquid carrier is annon-aqueous liquid medium and the electrically conductive polymer issoluble in and is dissolved in the non-aqueous liquid medium. Suitablenon-aqueous liquid media include organic liquids that have a boilingpoint of less than 120° C., more typically, less than or equal to about100° C., selected, based on the choice of electrically conductivepolymer, from non-polar organic solvents, such as hexanes, cyclohexane,benzene, toluene, chloroform, and diethyl ether, polar aprotic organicsolvents, such as dichloromethane, ethyl acetate, acetone, andtetrahydrofuran, polar protic organic solvents, such as methanol,ethanol, and propanol, as well as mixtures of such solvents.

In one embodiment, the liquid carrier may optionally further comprise,based on 100 pbw of the polymer composition of the present invention,from greater than 0 pbw to about 15 pbw, more typically from about 1 pbwto about 10 pbw, of an organic liquid selected from high boiling polarorganic liquids, typically having a boiling point of at least 120° C.,more typically from diethylene glycol, meso-erythritol,1,2,3,4,-tetrahydroxybutane, 2-nitroethanol, glycerol, sorbitol,dimethyl sulfoxide, tetrahydrofurane, dimethyl formamide, and mixturesthereof.

The electrically conductive polymer component of the respective polymercomposition, polymer film, and/or electronic device of the presentinvention may comprise one or more homopolymers, one or more co-polymersof two or more respective monomers, or a mixture of one or morehomopolymers and one or more copolymers. The respective polymercomposition, polymer film, and electrically conductive polymer filmcomponent of the electronic device of the present invention may eachcomprise a single polymer or may comprise a blend two or more polymerswhich differ from each other in some respect, for example, in respect tocomposition, structure, or molecular weight.

In one embodiment, the electrically conductive polymer of the respectivepolymer composition, polymer film, and/or electrically conductivepolymer film component of the electronic device of the present inventioncomprises one or more polymers selected from polythiophene polymers,poly(selenophene) polymers, poly(telurophene) polymers, polypyrrolepolymers, polyaniline polymers, fused polycylic heteroaromatic polymers,and blends of any such polymers.

In one embodiment, the electrically conductive polymer comprises one ormore polymers selected from electrically conductive polythiophenepolymers, electrically conductive poly(selenophene) polymers,electrically conductive poly(telurophene) polymers, and mixturesthereof. Suitable polythiophene polymers, poly(selenophene) polymers,poly(telurophene) polymers and methods for making such polymers aregenerally known. In one embodiment, the electrically conductive polymercomprises at least one polythiophene polymer, poly(selenophene) polymer,or poly(telurophene) polymer that comprises 2 or more, more typically 4or more, monomeric units according to structure (I) per molecule of thepolymer:

wherein:

Q is S, SE, or Te, more typically, S, and

each occurrence of R¹¹ and each occurrence of R¹² is independently H,alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonicacid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, hydroxy,hydroxyalkyl, benzyl, carboxylate, ether, ether carboxylate,amidosulfonate, ether sulfonate, ester sulfonate, and urethane, or boththe R¹ group and R² group of a given monomeric unit are fused to form,together with the carbon atoms to which they are attached, an alkyleneor alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring, which ring may optionally include one or more divalentnitrogen, selenium, telurium, sulfur, or oxygen atoms.

In one embodiment, Q is S, the R¹¹ and R¹² of the monomeric unitaccording to structure (I) are fused and the electrically conductivepolymer comprises a polydioxythiopene polymer that comprises 2 or more,more typically 4 or more, monomeric units according to structure (I.a)per molecule of the polymer:

wherein:

Q is S, SE, or Te, more typically, S,

each occurrence of R¹³ is independently H, alkyl, hydroxy, heteroalkyl,alkenyl, heteroalkenyl, hydroxalkyl, amidosulfonate, benzyl,carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate,or urethane, and

m′ is 2 or 3.

In one embodiment, all R¹³ groups of the monomeric unit according tostructure (I.a) are each H, alkyl, or alkenyl. In one embodiment, atleast one R¹³ groups of the monomeric unit according to structure (I.a)is not H. In one embodiment, each R¹³ groups of the monomeric unitaccording to structure (I.a) is H.

In one embodiment, the electrically conductive polymer comprises apolythiophene homopolymer of monomeric units according to structure(I.a) wherein each R¹³ is H and m′ is 2, known aspoly(3,4-ethylenedioxythiophene), more typically referred to as “PEDOT”.

In one embodiment, the electrically conductive polymer comprises one ormore polypyrrole polymers. Suitable polypyrrole polymers and methods formaking such polymers are generally known. In one embodiment, theelectrically conductive polymer comprises a polypyrrole polymer thatcomprises 2 or more, more typically 4 or more, monomeric units accordingto structure (II) per molecule of the polymer:

wherein:

each occurrence of R²¹ and each occurrence of R²² is independently H,alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonicacid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, hydroxy,hydroxyalkyl, benzyl, carboxylate, ether, amidosulfonate, ethercarboxylate, ether sulfonate, ester sulfonate, and urethane, or the R²¹and R²² of a given pyrrole unit are fused to form, together with thecarbon atoms to which they are attached, an alkylene or alkenylene chaincompleting a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, whichring may optionally include one or more divalent nitrogen, sulfur oroxygen atoms, and

each occurrence of R²³ is independently selected so as to be the same ordifferent at each occurrence and is selected from hydrogen, alkyl,alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino,epoxy, silane, siloxane, hydroxy, hydroxyalkyl, benzyl, carboxylate,ether, ether carboxylate, ether sulfonate, ester sulfonate, andurethane.

In one embodiment, each occurrence of R²¹ and each occurrence of R²² isindependently H, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl,hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, amidosulfonate, ethercarboxylate, ether sulfonate, ester sulfonate, urethane, epoxy, silane,siloxane, or alkyl, wherein the alky group may optionally be substitutedwith one or more of sulfonic acid, carboxylic acid, acrylic acid,phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl,epoxy, silane, or siloxane moieties.

In one embodiment, each occurrence of R²³ is independently H, alkyl, andalkyl substituted with one or more of sulfonic acid, carboxylic acid,acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano,hydroxyl, epoxy, silane, or siloxane moieties.

In one embodiment, each occurrence of R²¹, R²² and R²³ is H.

In one embodiment, R²¹ and R²² are fused to form, together with thecarbon atoms to which they are attached, a 6- or 7-membered alicyclicring, which is further substituted with a group selected from alkyl,heteroalkyl, hydroxy, hydroxyalkyl, benzyl, carboxylate, ether, ethercarboxylate, ether sulfonate, ester sulfonate, and urethane. In oneembodiment, and R²² are fused to form, together with the carbon atoms towhich they are attached, a 6- or 7-membered alicyclic ring, which isfurther substituted with an alkyl group. In one embodiment, R²¹ and R²²are fused to form, together with the carbon atoms to which they areattached, a 6- or 7-membered alicyclic ring, which is furthersubstituted with an alkyl group having at least 1 carbon atom.

In one embodiment, R²¹ and R²² are fused to form, together with thecarbon atoms to which they are attached, a —O—(CHR²⁴)n′-O— group,wherein:

each occurrence of R²⁴ is independently H, alkyl, hydroxy, hydroxyalkyl,benzyl, carboxylate, amidosulfonate, ether, ether carboxylate, ethersulfonate, ester sulfonate, and urethane, and

n′ is 2 or 3.

In one embodiment, at least one R²⁴ group is not hydrogen. In oneembodiment, at least one R²⁴ group is a substituent having F substitutedfor at least one hydrogen. In one embodiment, at least one Y group isperfluorinated.

In one embodiment, the electrically conductive polymer comprises one ormore polyaniline polymers. Suitable polyaniline polymers and methods ofmaking such polymers are generally known. In one embodiment, theelectrically conductive polymer comprises a polyaniline polymer thatcomprises 2 or more, more typically 4 or more, monomeric units selectedfrom monomeric units according to structure (III) and monomeric unitsaccording to structure (III.a) per molecule of the polymer:

wherein:

each occurrence of R³¹ and R³² s independently alkyl, alkenyl, alkoxy,cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl,alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkylsubstituted with one or more of sulfonic acid, carboxylic acid, halo,nitro, cyano or epoxy moieties, or two R³¹ or R³² groups on the samering may be fused to form, together with the carbon atoms to which theyare attached, a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring,which ring may optionally include one or more divalent nitrogen, sulfuror oxygen atoms, and

each a and a′ is independently an integer from 0 to 4,

each b and b′ is integer of from 1 to 4, wherein, for each ring, the sumof the a and b coefficients of the ring or the a′ and b′ coefficients ofthe ring is 4.

In one embodiment, a or a′═O and the polyaniline polymer is annon-substituted polyaniline polymers referred to herein as a “PANI”polymer.

In one embodiment, the electrically conductive polymer comprises one ormore polycylic heteroaromatic polymers. Suitable polycylicheteroaromatic polymers and methods for making such polymers aregenerally known. In one embodiment, the electrically conductive polymercomprises one or more polycylic heteroaromatic polymers that comprise 2or more, more typically 4 or more, monomeric units per molecule that arederived from one or more heteroaromatic monomers, each of which isindependently according to Formula (IV):

wherein:

Q is S or NH,

R⁴¹, R⁴², R⁴³, and R⁴⁴ are each independently H, alkyl, alkenyl, alkoxy,alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl,amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl,alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl,acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano,hydroxyl, epoxy, silane, siloxane, hydroxy, hydroxyalkyl, benzyl,carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate,ester sulfonate, or urethane, provided that at least one pair ofadjacent substituents R⁴¹ and R⁴², R⁴² and R⁴³, or R⁴³ and R⁴⁴ are fusedto form, together with the carbon atoms to which they are attached, a 5or 6-membered aromatic ring, which ring may optionally include one ormore hetero atoms, more typically selected from divalent nitrogen,sulfur and oxygen atoms, as ring members.

In one embodiment, the polycylic heteroaromatic polymers comprise 2 ormore, more typically 4 or more, monomeric units per molecule that arederived from one or more heteroaromatic monomers, each of which isindependently according to structure (V):

wherein:

Q is S, Se, Te, or NR⁵⁵,

T is S, Se, Te, NR⁵⁵, O, Si(R⁵⁵)₂, or PR⁵⁵,

E is alkenylene, arylene, and heteroarylene,

R⁵⁵ is hydrogen or alkyl,

R⁵¹, R⁵², R⁵³, and R⁵⁴ are each independently H, alkyl, alkenyl, alkoxy,alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl,amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl,alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl,acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile,cyano, hydroxyl, epoxy, silane, siloxane, hydroxy, hydroxyalkyl, benzyl,carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate,and urethane, or where each pair of adjacent substituents R⁵¹ and R⁵²and adjacent substituents R⁵³ and R⁵⁴ may independently form, togetherwith the carbon atoms to which they are attached, a 3, 4, 5, 6, or7-membered aromatic or alicyclic ring, which ring may optionally includeone or more hetero atoms, more typically selected from divalentnitrogen, sulfur and oxygen atoms, as ring members.

In one embodiment, the electrically conductive polymer comprises one ormore copolymers that each comprise at least one first monomeric unit permolecule that is according to formula (I), (I.a), (II), (III), or(III.a) or that is derived from a heteroaromatic monomer according tostructure (IV) or (V), and further comprises one or more secondmonomeric units per molecule that differ in structure and/or compositionfrom the first monomeric units. Any type of second monomeric units canbe used, so long as it does not detrimentally affect the desiredproperties of the copolymer. In one embodiment, the copolymer comprises,based on the total number of monomer units of the copolymer, less thanor equal to 50%, more typically less than or equal to 25%, even moretypically less than or equal to 10% of second monomeric units.

Exemplary types of second monomeric units include, but are not limitedto those derived from alkenyl, alkynyl, arylene, and heteroarylenemonomers, such as, for example, fluorene, oxadiazole, thiadiazole,benzothiadiazole, phenylene vinylene, phenylene ethynylene, pyridine,diazines, and triazines, all of which may be further substituted, thatare copolymerizable with the monomers from which the first monomericunits are derived.

In one embodiment, the copolymers are made by first forming anintermediate oligomer having the structure A-B-C, where A and Crepresent first monomeric units, which can be the same or different, andB represents a second monomeric unit. The A-B-C intermediate oligomercan be prepared using standard synthetic organic techniques, such asYamamoto, Stille, Grignard metathesis, Suzuki and Negishi couplings. Thecopolymer is then formed by oxidative polymerization of the intermediateoligomer alone, or by copolymerization of the intermediate oligomer withone or more additional monomers.

In one embodiment, the electrically conductive polymer comprises atleast one homopolymer of a monomer selected from thiophene monomers,pyrrole monomers, aniline monomers, and polycyclic aromatic monomers,more typically a poly(thiophene) homopolymer. In one embodiment, theelectrically conductive polymer comprises at least one copolymer of twoor more monomers wherein at least one of such monomers is selected fromthiophene monomers, pyrrole monomers, aniline monomers, and polycyclicaromatic monomers.

In one embodiment, the weight average molecular weight of theelectrically conductive polymer is from about 1000 to about 2,000,000grams per mole, more typically from about 5,000 to about 1,000,000 gramsper mole, and even more typically from about 10,000 to about 500,000grams per mole.

In one embodiment, the electrically conductive polymer further comprisesa polyanion, such as a polymer acid dopant, typically (particularlywhere the liquid medium of the polymer composition is an aqueousmedium), a water soluble polymer acid dopant. In one embodiment, theelectrically conductive polymers used in the new compositions andmethods are prepared by oxidatively polymerizing the correspondingmonomers in aqueous solution containing a water soluble acid, typicallya water-soluble polymer acid. In one embodiment, the acid is a polymersulfonic acid. Some non-limiting examples of the acids are polysulfonicacid polymers, such as for example, poly(styrenesulfonic acid) (“PSSA”),polyvinylsulfonic acid, and poly(2-acrylamido-2-methyl-1-propanesulfonicacid) (“PAAMPSA”), and polycarboxylic acid polymers, such as forexample, poly(acrylic acid), poly(methacrylic acid), and poly(maleicacid), as well as mixtures thereof. The acid anion provides the dopantfor the conductive polymer. In one embodiment, the electricallyconductive polymer comprises a cationic electrically conductive polymerand a polyanion. The oxidative polymerization is carried out using anoxidizing agent such as ammonium persulfate, sodium persulfate, andmixtures thereof. Thus, for example, when aniline is oxidativelypolymerized in the presence of PMMPSA, the doped electrically conductivepolymer blend PANI/PAAMPSA is formed. When ethylenedioxythiophene (EDT)is oxidatively polymerized in the presence of PSSA, the dopedelectrically conductive polymer blend PEDT/PSS is formed. The conjugatedbackbone of PEDT is partially oxidized and positively charged.Oxidatively polymerized pyrroles and thienothiophenes also have apositive charge which is balanced by the acid anion.

In one embodiment, the water soluble polymer acid selected from thepolysulphonic acids, more typically, polystyrene sulfonic acid), orpoly(acrylamido-2-methyl-1-propane-sulfonic acid), or a polycarboxylicacid, such as polyacrylic acid, polymethacrylic acid, or polymaleicacid. The polymer acid typically has a weight average molecular weightof from about 1,000 to about 2,000,000 grams per mole (g/mole), moretypically of from about 2,000 to about 1,000,000 g/mole.

In one embodiment, the electrically conductive polymer component of therespective polymer film, polymer gel, polymer foam, polymer composition,and/or electronic device of the present invention comprises, based on100 pbw of the electrically conductive polymer:

-   (i) from greater than 0 pbw to 100 pbw, more typically from about 10    to about 50 pbw, and even more typically from about 20 to about 50    pbw, of one or more electrically conductive polymers, more typically    of one or more electrically conductive polymer comprising monomeric    units according to structure (I.a), more typically one or more    polythiophene polymers comprising monomeric units according to    structure (I.a) wherein Q is S, and even more typically of one or    more electrically conductive polymers comprising    poly(3,4-ethylenedioxythiophene), and-   (ii) from 0 pbw to 100 pbw, more typically from about 50 to about 90    pbw, and even more typically from about 50 to about 80 pbw, of one    or more water soluble polymer acid dopants, more typically of one or    more water soluble polymer acid dopants comprising a poly(styrene    sulfonic acid) dopant.

Ionic liquids are organic salts that consist entirely of anionic andcationic species and have a melting point of less than or equal to 100°C. In one embodiment, the ionic liquid has a melting point of less thanor equal to 75° C., more typically less than or equal to 50° C. and evenmore typically less than or equal to 25° C.

In one embodiment, the ionic liquid comprises one or more organic saltsthat consist entirely of anionic and cationic species and have a meltingpoint of less than or equal to 100° C.

In one embodiment, the cation of a ionic liquid compound is a bulky,asymmetrical organic moiety. Typical cations for suitable ionic liquidcompounds include, for example:

ammonium or tetraalkyl ammonium cations, such as, for example,tetramethyl ammonium, tetrabutyl ammonium, tetrahexyl ammonium,butyltrimethyl ammonium, and methyltrioctyl ammonium cations,

guanidinium cations such as, for example,N,N,N′,N′-tetrahexyl-N″,N″-dimethylguanidinium cations,

imidazolium cations, more typically, imidazolium cations that aresubstituted with from 1 to 3, more typically 2 to 3, alkyl,hydroxyalkyl, and/or aryl substituents per boron atom, such as, forexample, 1,3-dimethyl-imidazolium, 1-benzyl-3-methyl-imidazolium,1-butyl-3-methyl-imidazolium, 1-ethyl-3-methyl-imidazolium,1-hexyl-3-methyl-imidazolium, 1-methyl-3-propyl-imidazolium,1-methyl-3-octyl-imidazolium, 1-methyl-3-tetradecyl-imidazolium,1-methyl-3-phenyl-imidazolium, 1,2,3-trimethyl-imidazolium,1,2-methyl-3-octyl-imidazolium, 1-butyl-2,3-dimethyl-imidazolium,1-hexyl-2,3-methyl-imidazolium, and1-(2-hydroxyethyl)-2,3-dimethyl-imidazolium cations,

morpholinium cations, such as, for example, N-methyl-morpholinium andN-ethyl-morpholinium cations,

phosphonium cations, such as for example, tetrabutyl phosphonium andtributylmethyl phosphonium cations,

piperidinium cations, such as, for example,1-butyl-1-methyl-piperidinium and 1-methyl-1-propyl-piperidiniumcations,

pyradazinium cations,

pyrazinium cations, such as, for example, 1-ethyl-4-methyl-pyrazinium,1-octyl-4-propyl-pyrazinium cations,

pyrazolium cations, such as, for example, 1-ethyl-2,3,5-pyrazoliniumcations,

pyridinium cations, such as for example, N-butyl-pyridinium, andN-hexyl-pyridinium cations,

pyrimidinium cations, such as, for example,1-hexyl-3-propyl-pyrimidinium, 1-ethyl-3-methyl-pyrimidinium cations,

pyrrolidinium cations, such as for example,1-butyl-1-methyl-pyrrolidinium and 1-methyl-1-propyl-pyrrolidiniumcations,

pyrrolium cations, such as for example, 1,1-dimethyl-pyrrolium,1-methyl-1-pentyl-pyrrolium cations,

pyrrolinium cations,

sulfonium cations, such as, for example, trimethyl sulfonium cations,

thiazolium cations,

oxazolium cations, and

triazolium cations.

Typical anions for suitable ionic liquid compounds include, for example:

borate anions, such as, for example, tetrafluoroborate,tetracyanoborate, tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, alkyltrifluoroborate,perfluoroalkyltrifluoroborate, and alkenyltrifluoroborate anions

carbonate anions such as, for example, hydrogen carbonate andmethylcarbonate anions,

carboxylate anions, such as, for example, salicylate, thiosalicylate,L-lactate, acetate, trifluoroacetate, and formate anions,

chlorate anions,

cyanate anions, such as, for example, thiocyanate, dicyanamide, andtricyanomethane anions,

halide anions, such as, for example, fluoride, chloride, bromide, andiodide anions,

imide anions, such as, for example, imide andbis(fluoromethylsulfonyl)imide anions,

nitrate anions,

phosphate anions, such as, for example, dihydrogen phosphate,hexafluorophosphate, di(trifluoromethyl)tetrafluorophosphate,tris(trifluoromethyl)trifluorophosphate,tris(perfluoroalkyl)trifluorophosphate,tetra(trifluoromethyl)difluorophosphate,penta(trifluoromethyl)fluorphosphate, and hexa(trifluoromethylphosphateanions,

sulfate and sulfonate anions, such as, for example,trifluoromethanesulfonate, hydrogen sulfate, tosylate,(C₁-C₁₂)alkylsulfate, and (C₁-C₁₂)alkylsulfonate anions,

perfluoroalkyl β-diketonate anions, such as, for example,6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate,1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, and4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate anions,

fluorohydrogenate anions, such as, for example, poly(hydrogen fluoride)fluoride anions, and

fluorometallate anions, such as, for example, oxopentafluorotungstan(VI) anions.

The ionic liquid may comprise a mixture of ionic liquid compounds andthus a mixture of two or more of such cations and/or two or more of suchanions.

The cation and anion of the ionic liquid are selected, according totechniques known in the art, to tailor the properties of the ionicliquid to suit the demands of the particular application, for example anionic liquid with an imidazolium cation would typically be expected toprovide lower viscosity and higher conductivity, but lower stability,than an analogous ionic liquid with ammonium or pyrrolidium cation, andan ionic liquid with a smaller anion, such as dicyanamide andtetracyanoborate anions, would typically be expected to provide higherconductivity, but lower stability, than an analogous ionic liquid with alarger anion, such as a tris(pentafluoroethyl)trifluorophosphate anion.

In one embodiment, the ionic liquid is an ionic compound that has amelting point of less than or equal to 25° C., such as, for example,1-ethyl-3-methyl-imidazolium tetrachloroaluminate,1-butyl-3-methyl-imidazolium tetrachloroaluminate,1-ethyl-3-methyl-imidazolium acetate, 1-butyl-3-methyl-imidazoliumacetate, 1-ethyl-3-methyl-imidazolium ethylsulfate,1-butyl-3-methyl-imidazolium methylsulfate, 1-ethyl-3-methyl-imidazoliumthiocyanate, 1-butyl-3-methyl-imidazolium thiocyanate,1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide,1-ethyl-3-methyl-imidazolium tetracyanoborate,1-butyl-1-methyl-pyrrolidinium dicyanamide, 1-ethyl-3-methyl-imidazoliumtetrafluoroborate, 1-ethyl-3-methyl-imidazolium trifluoroacetate,1-ethyl-3-methyl-imidazolium bis(fluoromethylsulfonyl)imide, andmixtures thereof.

In one embodiment, the ionic liquid is an ionic compound that has amelting point of less than 25° C., a viscosity at 20° C. of less than orequal to about 100 centiPoise, and a specific conductance of greaterthan or equal to about 5 milliSiemens per centimeter (“mS/cm”), moretypically greater than 10 mS/cm, such as, for example,1-ethyl-3-methyl-imidazolium tetracyanoborate,1-butyl-1-methyl-pyrrolidinium dicyanamide, 1-ethyl-3-methyl-imidazoliumtetrafluoroborate, 1-ethyl-3-methyl-imidazolium thiocyanate,1-ethyl-3-methyl-imidazolium trifluoroacetate, and1-ethyl-3-methyl-imidazolium bis(fluoromethylsulfonyl)imide, andmixtures thereof.

In one embodiment, the ionic liquid comprises a salt of an alkyl-,hydroxyalkyl- and/or aryl-substituted imidazolium cation and a cyanateanion, such as, for example, 1,3-dimethyl-imidazolium dicyanate,1-benzyl-3-methyl-imidazolium thiocyanate, 1-butyl-3-methyl-imidazoliumtricyanomethane, 1-ethyl-3-methyl-imidazolium dicyanate,1-hexyl-3-methyl-imidazolium thiocyanate, 1-methyl-3-propyl-imidazoliumtricyanomethane, 1-methyl-3-octyl-imidazolium dicyanate,1-methyl-3-tetradecyl-imidazolium thiocyanate,1-methyl-3-phenyl-imidazolium dicyanate, 1,2,3-trimethyl-imidazoliumthiocyanate, 1,2-methyl-3-octyl-imidazolium tricyanomethane,1-butyl-2,3-dimethyl-imidazolium dicyanate,1-hexyl-2,3-methyl-imidazolium thiocyanate, and1-(2-hydroxyethyl)-2,3-dimethyl-imidazolium tricyanomethane, andmixtures thereof.

In one embodiment, the ionic liquid comprises a salt of an alkyl-,hydroxyalkyl- and/or aryl-substituted imidazolium cation and atetracyanoborate anion, such as, for example, 1,3-dimethyl-imidazoliumtetracyanoborate, 1-benzyl-3-methyl-imidazolium tetracyanoborate,1-butyl-3-methyl-imidazolium tetracyanoborate,1-ethyl-3-methyl-imidazolium tetracyanoborate,1-hexyl-3-methyl-imidazolium tetracyanoborate,1-methyl-3-propyl-imidazolium tetracyanoborate,1-methyl-3-octyl-imidazolium tetracyanoborate,1-methyl-3-tetradecyl-imidazolium tetracyanoborate,1-methyl-3-phenyl-imidazolium tetracyanoborate,1,2,3-trimethyl-imidazolium tetracyanoborate,1,2-methyl-3-octyl-imidazolium tetracyanoborate,1-butyl-2,3-dimethyl-imidazolium tetracyanoborate,1-hexyl-2,3-methyl-imidazolium tetracyanoborate, and1-(2-hydroxyethyl)-2,3-dimethyl-imidazolium tetracyanoborate, andmixtures thereof.

In one embodiment, the ionic liquid comprises a salt of an alkyl-,hydroxyalkyl- and/or aryl-substituted imidazolium cation and atetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borateanion, such as, for example, 1,3-dimethyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1-benzyl-3-methyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1-butyl-3-methyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1-ethyl-3-methyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1-hexyl-3-methyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1-methyl-3-propyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1-methyl-3-octyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1-methyl-3-tetradecyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1-methyl-3-phenyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1,2,3-trimethyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1,2-methyl-3-octyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,1-butyl-2,3-dimethyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,2H-perfluorooctyl)silyl)phenyl)borate, 1-hexyl-2,3-methyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,and 1-(2-hydroxyethyl)-2,3-dimethyl-imidazoliumtetrakis-(p-(dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl)phenyl)borate,and mixtures thereof.

In one embodiment, the ionic liquid comprises a salt of an alkyl-,hydroxyalkyl- and/or aryl-substituted imidazolium cation and ahexafluorophosphate anion, such as, for example,1,3-dimethyl-imidazolium hexyluorophosphate,1-benzyl-3-methyl-imidazolium hexyluorophosphate,1-butyl-3-methyl-imidazolium hexyluorophosphate,1-ethyl-3-methyl-imidazolium hexyluorophosphate,1-hexyl-3-methyl-imidazolium hexyluorophosphate,1-methyl-3-propyl-imidazolium hexyluorophosphate,1-methyl-3-octyl-imidazolium hexyluorophosphate,1-methyl-3-tetradecyl-imidazolium hexyluorophosphate,1-methyl-3-phenyl-imidazolium hexyluorophosphate,1,2,3-trimethyl-imidazolium hexyluorophosphate,1,2-methyl-3-octyl-imidazolium hexyluorophosphate,1-butyl-2,3-dimethyl-imidazolium hexyluorophosphate,1-hexyl-2,3-methyl-imidazolium hexyluorophosphate, and1-(2-hydroxyethyl)-2,3-dimethyl-imidazolium hexyluorophosphate, andmixtures thereof.

As mentioned above, U.S. Pat. No. 7,438,832, issued Oct. 21, 2008broadly discloses mixtures of electrically conductive polymers and ionicliquids, including specifically, mixtures of PEDOT-PSS and1-butyl-3-methyl-imidazolium tetrafluoroborate. In one embodiment,wherein the electrically conductive polymer component of the respectivepolymer film, polymer composition, and/or electronic device of thepresent invention comprises a blend of a poly(thophene) polymer and awater soluble acid polymer, or more typically ofpoly(3,4-ethylenedioxythiophene) and poly(styrene sulfonic acid), theionic liquid component of such polymer film, polymer composition, and/orelectronic device does not comprise 1-butyl-3-methyl-imidazoliumtetrafluoroborate, or, more typically the ionic liquid component of suchpolymer film, polymer composition, and/or electronic device does notcomprise a tetrafluoroborate anion.

In one embodiment, the ionic liquid component of the respective polymerfilm, polymer composition, and/or electronic device of the presentinvention does not comprise a tetrafluoroborate anion.

As mentioned above, U.S. Pat. No. 7,842,197, issued Nov. 30, 2010,discloses a method for producing a conductive material by contacting anelectrically conductive polymer with certain ionic liquids, includingspecifically, contacting PEDOT-PSS and iodidated1-hexyl-3-methylimidazolium or bis(trifluoromethane sulfonic acid)imide1-ethyl-3-methylimidazolium. In one embodiment, wherein the electricallyconductive polymer component of the respective polymer film, polymergel, polymer foam, polymer composition, and/or electronic device of thepresent invention is a blend of a poly(thiophene) polymer and a watersoluble acid polymer, the, ionic liquid component of such polymer film,polymer composition, and/or electronic device does not compriseiodidated 1-hexyl-3-methylimidazolium or bis(trifluoromethane sulfonicacid)imide 1-ethyl-3-methylimidazolium, more typically does not comprisea para-toluene sulfonate anion, tetrafluoroborate anion,bis(trifluoromethylsulfonyl)imide anion, (CF₃SO₃)⁻ anion,(CH₃CH₂CH₂CH₂SO₃)⁻ anion, or (CHF₂CF₂CF₂CF₂CH₂SO₃)⁻ anion, and, evenmore typically, does not comprise a sulfonate anion, sulfate anion,carboxylate anion, bis(trifluoromethylsulfonyl)imide anion, nitrateanion, nitro anion, halogen anion, PF₆ ⁻ anion, or tetrafluoroborateanion.

In one embodiment, ionic liquid component of the respective polymerfilm, polymer gel, polymer foam, polymer composition, and/or electronicdevice of the present invention does not comprise a sulfonate anion,tetrafluoroborate anion, sulfonylimide anion,bis(trifluoromethylsulfonyl)imide anion, more typically the ionic liquidcomponent of the respective polymer film, polymer gel, polymer foam,polymer composition, and/or electronic device of the present inventiondoes not comprise a sulfonate anion, sulfate anion, carboxylate anion,bis(trifluoromethylsulfonyl)imide anion, nitrate anion, nitro anion,halogen anion, PF₆ ⁻ anion, or tetrafluoroborate anion.

The respective polymer composition, polymer film, and polymer filmcomponent of the electronic device of the present invention may eachoptionally further comprise one or more additional components, such as,for example one or more of polymers, dyes, coating aids, conductiveparticles, conductive inks, conductive pastes, charge transportmaterials, crosslinking agents, and combinations thereof, that aredissolved or dispersed in the liquid carrier.

The polymer composition, polymer film, and polymer film component of theelectronic device of the present invention may each optionally furthercomprise one or more electrically conductive additives, such as, forexample, metal particles, including metal nanoparticles and metalnanowires, graphite particles, including graphite fibers, or carbonparticles, including carbon fullerenes and carbon nanotubes, and as wellas combinations of any such additives. Suitable fullerenes include forexample, C60, C70, and C84 fullerenes, each of which may be derivatized,for example with a (3-methoxycarbonyl)-propyl-phenyl (“PCBM”) group,such as C60-PCBM, C-70-PCBM and C-84 PCBM derivatized fullerenes.Suitable carbon nanotubes include single wall carbon nanotubes having anarmchair, zigzag or chiral structure, as well as multiwall carbonnanotubes, including double wall carbon nanotubes, and mixtures thereof.

In one embodiment, the respective polymer film of the present inventionand polymer film component of the electronic device of the presentinvention further each comprise up to about 65 pbw, more typically fromabout 12 to about 62 pbw carbon particles, more typically carbonnanotubes, and even more typically multi-wall carbon nanotubes, per 100pbw of the film.

In one embodiment, the polymer composition of the present invention ismade by providing a solution or dispersion of the electricallyconductive polymer in the liquid carrier or dissolving or dispersing theelectrically conductive polymer in the liquid carrier and dissolving ordispersing the ionic liquid in the liquid carrier, typically by addingthe electrically conductive polymer and ionic liquid to the liquidcarrier and agitating the mixture, more typically by providing asolution or dispersion of an electrically conductive polymer in a liquidcarrier and dissolving or dispersing an ionic liquid in the solution ordispersion of the electrically conductive polymer in the liquid carrier.

In one embodiment, the ionic liquid is added to a quiescent, that is,without mixing, aqueous solution or dispersion of the electricallyconductive polymer in the liquid carrier and then mixed. In anotherembodiment, an aqueous solution or dispersion of electrically conductivepolymer in the liquid carrier is mixed and the ionic liquid is added tothe aqueous dispersion of the electrically conductive polymer in theliquid carrier with continued mixing. In forming gel versions of thecomposition of the present invention, adding ionic liquid to a quiescentaqueous solution or dispersion of the electrically conductive polymer inthe liquid carrier and then mixing tends to result in immediategelation, while mixing the aqueous solution or dispersion ofelectrically conductive polymer in the liquid carrier and adding theionic liquid to the aqueous dispersion of the electrically conductivepolymer in the liquid carrier with continued mixing tends to delaygelation.

In one embodiment, an electrically conductive polymer film according tothe present invention is made from the polymer composition of thepresent invention by depositing a layer of the polymer composition by,for example, casting, spray coating, spin coating, gravure coating,curtain coating, dip coating, slot-die coating, ink jet printing,gravure printing, or screen printing, on a substrate and removing theliquid carrier from the layer. Typically, the liquid carrier is removedfrom the layer by allowing the liquid carrier component of the layer toevaporate. The substrate supported layer may be subjected to elevatedtemperature to encourage evaporation of the liquid carrier.

The substrate may be rigid or flexible and may comprise, for example, ametal, a polymer, a glass, a paper, or a ceramic material. In oneembodiment, the substrate is a flexible plastic sheet. In oneembodiment, the substrate is a flexible plastic sheets comprising apolymer selected from polyesters, polysulfones, polyethersulfones,polyarylates, polyimides, polyetherimides, polytetrafluoroethylenes,poly(ether ketone)s, poly(ether ether ketone)s, poly((meth)acrylate)s,polycarbonates, polyolefins, and mixture thereof.

The polymer film may cover an area of the substrate that is as large asan entire electronic device or as small as a specific functional areasuch as the actual visual display, or as small as a single sub-pixel. Inone embodiment, the polymer film has a thickness of from greater than 0to about 10 μm, more typically from 0 to about 50 nm.

In an alternative embodiment, the polymer film of the present inventionis made by contacting a film of electrically conductive polymer,typically supported on a substrate, with the ionic liquid. The polymerfilm may be contacted with the ionic liquid by, for example, immersingthe polymer film in a volume of the ionic liquid or by applying a layerof the ionic liquid to a surface of the film, such as, for example, byspray application. The time and temperature of contacting may bedetermined on a case by case basis, depending upon the identity ofpolymer, the identity of the ionic liquid, the geometry of the film, andthe desired result. Typically the contacting is conducted at roomtemperature or at an elevated temperature, typically of up to about 100°C. The contact time may be any non-zero contact time, more typically thecontact time is from about 1 minute to about one hour. Following thecontacting step, any excess ionic liquid may be removed by washing thepolymer film with a suitable liquid medium, such as for example, water,an organic solvent, or a mixture of water and water miscible organicsolvent.

In one embodiment, the polymer film of the present invention is notredispersible in the liquid carrier, and the film can thus be applied asa series of multiple thin films. In addition, the film can be overcoatedwith a layer of different material dispersed in the liquid carrierwithout being damaged.

In one embodiment, the electrically conductive foam of the presentinvention is made by contacting, in an aqueous liquid medium, theelectrically conductive polymer with an amount of ionic liquid effectiveto gel the electrically conductive polymer, and removing the aqueousliquid medium from the gel to form the polymer foam. In one embodiment,the liquid medium is removed form the gel by freeze-drying the gel.

In one embodiment, the polymer composition of the present inventioncomprises, based on 100 pbw of the polymer composition:

-   (a) from greater than 0 to less than 100 pbw, more typically from    about 50 to less than 100 pbw, even more typically from about 90 to    about 99.5 pbw of a liquid carrier,-   (b) from greater than 0 to less than 100 pbw, more typically from    greater than 0 to about 50 pbw, even more typically from 0.5 to    about 10 pbw, of an electrically conductive polymer and an ionic    liquid, comprising, based on 100 pbw of the total amount of the    electrically conductive polymer and the ionic liquid,    -   (i) from about 1 to about 99.9 pbw, more typically from about 2        to about 99.9 pbw, and even more typically from about 25 to        about 80 pbw of the electrically conductive polymer, said        electrically conductive polymer comprising, based on 100 pbw of        the electrically conductive polymer:        -   (1) from greater than 0 pbw to 100 pbw, more typically from            about 10 to about 50 pbw, and even more typically from about            20 to about 50 pbw of one or more electrically conductive            polymers, more typically one or more electrically conductive            polymers comprising monomeric units according to structure            (I.a), even more typically one or more polythiophene            polymers comprising monomeric units according to structure            (I.a) wherein Q is S, and even more typically one or more            electrically conductive polymers comprising            poly(3,4-ethylenedioxythiophene), and        -   (2) from 0 pbw to 100 pbw, more typically from about 50 to            about 90 pbw, and even more typically from about 50 to about            80 pbw, of one or more water soluble polymer acid dopants,            more typically of one or more water soluble polymer acid            dopants comprising a poly(styrene sulfonic acid) dopant, and    -   (ii) from about 0.1 to about 99 pbw, more typically from about        0.1 to about 97.5 pbw, and even more typically from about 20 to        about 75 pbw of the ionic liquid, said ionic liquid comprising a        cyanate anion, a tetracyanoborate anion, a        tetrakis-(p-(dimethyl(1H, 1H, 2H,        2H-per-fluorooctyl)silyl)phenyl)borate anion, or a        hexafluorophosphate anion, more typically comprising a salt of        an alkyl-, hydroxyalkyl-, and/or aryl-substituted imidazolium        cation and a cyanate anion, a tetracyanoborate anion, a        tetrakis-(p-(dimethyl(1H, 1H, 2H,        2H-per-fluorooctyl)silyl)phenyl)borate anion, or a        hexafluorophosphate anion, and even more typically comprising        1-ethyl-3-methyl-imidazolium dicyanate,        1-ethyl-3-methyl-imidazolium tetracyanoborate,        1-ethyl-3-methyl-imidazolium tetrakis-(p-(dimethyl(1H, 1H, 2H,        2H-per-fluorooctyl)silyl)phenyl)borate anion, or        1-ethyl-3-methyl-imidazolium tetracyanoborate        hexafluorophosphate, even more typically        1-ethyl-3-methyl-imidazolium tetracyanoborate.

In one embodiment, the respective polymer film the present inventionand/or polymer film component of the electronic device of the presentinvention each comprise, based on 100 pbw of the polymer film:

-   (a) from about 1 to about 99.9 pbw, more typically from about 2 to    about 99.9 pbw, and even more typically from about 10 to about 80    pbw of an electrically conductive polymer, said electrically    conductive polymer comprising, based on 100 pbw of the electrically    conductive polymer:    -   (1) from greater than 0 pbw to 100 pbw, more typically from        about 10 to about 50 pbw, and even more typically from about 20        to about 50 pbw of one or more electrically conductive polymers,        more typically one or more electrically conductive polymers        comprising monomeric units according to structure (I.a), more        typically one or more polythiophene polymers comprising        monomeric units according to structure (I.a) wherein Q is S, and        even more typically, one or more electrically conductive        polymers comprising poly(3,4-ethylenedioxythiophene), and    -   (2) from 0 pbw to 100 pbw, more typically from about 50 to about        90 pbw, and even more typically from about 50 to about 80 pbw,        of one or more water soluble polymer acid dopants, more        typically of one or more water soluble polymer acid dopants        comprising a poly(styrene sulfonic acid) dopant, and-   (b) from about 0.1 to about 99 pbw, more typically from about 0.1 to    about 97.5 pbw, and even more typically from about 20 to about 90    pbw of an ionic liquid, said ionic liquid comprising a cyanate    anion, a tetracyanoborate anion, a tetrakis-(p-(dimethyl(1H, 1H, 2H,    2H-per-fluorooctyl)silyl)phenyl)borate anion, or a    hexafluorophosphate anion, more typically comprising a salt of an    alkyl-, hydroxyalkyl-, and/or aryl-substituted imidazolium cation    and a cyanate anion, a tetracyanoborate anion, a    tetrakis-(p-(dimethyl(1H, 1H, 2H,    2H-per-fluorooctyl)silyl)phenyl)borate anion, or a    hexafluorophosphate anion, and even more typically comprising    1-ethyl-3-methyl-imidazolium dicyanate, 1-ethyl-3-methyl-imidazolium    tetracyanoborate, 1-ethyl-3-methyl-imidazolium    tetrakis-(p-(dimethyl(1H, 1H, 2H,    2H-per-fluorooctyl)silyl)phenyl)borate anion, or    1-ethyl-3-methyl-imidazolium tetracyanoborate hexafluorophosphate,    even more typically 1-ethyl-3-methyl-imidazolium tetracyanoborate.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each comprise, based on 100 pbw of the polymer film:

-   (a) from about 10 to about 80 pbw of an electrically conductive    polymer, comprising, based on 100 pbw of the electrically conductive    polymer:    -   (1) from about 20 to about 50 pbw of        poly(3,4-ethylenedioxythiophene), and    -   (2) from about 50 to about 80 pbw of poly(styrene sulfonic acid)        dopant, and-   (b) from about 20 to about 90 pbw of an ionic liquid comprising    1-ethyl-3-methyl-imidazolium dicyanate, 1-ethyl-3-methyl-imidazolium    tetracyanoborate, 1-ethyl-3-methyl-imidazolium    tetrakis-(p-(dimethyl(1H, 1H, 2H,    2H-per-fluorooctyl)silyl)phenyl)borate anion, or    1-ethyl-3-methyl-imidazolium tetracyanoborate hexafluorophosphate,    even more typically 1-ethyl-3-methyl-imidazolium tetracyanoborate.

The polymer film according to the present invention typically exhibitshigh conductivity and high optical transparency and is useful as a layerin an electronic device in which the high conductivity is desired incombination with optical transparency.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each exhibit a sheet resistance of less than or equal to 500Ohms per square (“Ω/□”). In another embodiment, the respective polymerfilm of the present invention and polymer film component of theelectronic device of the present invention each exhibit a sheetresistance of less than or equal to 300Ω/□. In another embodiment, therespective polymer film of the present invention and polymer filmcomponent of the electronic device of the present invention each exhibita sheet resistance of less than or equal to 200Ω/□, more typically lessthan or equal to 100Ω/□. The polymer film of the present inventionexhibits the above described sheet resistance values even in the absenceof electrically conductive particles, such as metal particles, graphiteparticles or carbon particles, and the sheet resistance of the polymerfilm may be further reduced by addition of such electrically conductiveparticles. In one embodiment, a polymer film that consists essentiallyof (that is, in the absence of any electrically conductive particles) amixture of the electrically conductive polymer and the ionic liquidexhibits sheet resistance of less than or equal to 500Ω/□, or less thanor equal to 300Ω/□, or less than or equal to 200Ω/□. In one embodiment,a polymer film that consists of a mixture of the electrically conductivepolymer and the ionic liquid exhibits a sheet resistance of less than orequal to 500Ω/□, or less than or equal to 300Ω/□, or less than or equalto 200Ω/□.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each exhibit an optical transmittance at 550 nm of greaterthan or equal to 90%, more typically greater than or equal to 93%, evenmore typically greater than or equal to 95%, and still more typically ofgreater than or equal to 98%.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each exhibit a sheet resistance of less than or equal to500Ω/□, or less than or equal to 300Ω/□, or less than or equal to200Ω/□, or less than or equal to 100Ω/□, and an optical transmittance at550 nm of greater than or equal to 90%, more typically greater than orequal to 93%, even more typically greater than or equal to 95% and stillmore typically of greater than or equal to 98%.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each exhibit a conductivity of greater than or equal to 500Siemens per centimeter (“S/cm”), more typically greater than or equal to1000 S/cm, even more typically greater than or equal to 1500 S/cm, andstill more typically greater than or equal to 2000 S/cm. Theconductivity of the film is calculated according to formula (1):σ=1/ρ_(s) t  (1)

wherein:

σ is the conductivity of the film, in Siemens per centimeter (“S/cm”),

ρ_(s) is the sheet resistance of the film, in Ohms per square (“Ω/□”),and

t is the thickness of the film, in centimeters (“cm”).

The polymer film of the present invention exhibits the above describedconductivity values even in the absence of electrically conductiveparticles, such as metal particles, graphite particles or carbonparticles, and the conductivity of the polymer film may be furtherreduced by addition of such electrically conductive particles. In oneembodiment, a polymer film that consists essentially of (that is, in theabsence of any electrically conductive particles) a mixture of theelectrically conductive polymer and the ionic liquid exhibitsconductivity of greater than or equal to 500 S/cm or greater than orequal to 1000 S/cm, or greater than or equal to 1500 S/cm or greaterthan or equal to 2000 S/cm. In one embodiment, a polymer film thatconsists of a mixture of the electrically conductive polymer and theionic liquid exhibits a conductivity of greater than or equal to 500S/cm or greater than or equal to 1000 S/cm, or greater than or equal to1500 S/cm or greater than or equal to 2000 S/cm.

In one embodiment, the respective polymer film of the present inventionand/or polymer film component of the electronic device of the presentinvention each exhibit a conductivity of greater than or equal to 500S/cm or greater than or equal to 1000 S/cm, or greater than or equal to1500 S/cm or greater than or equal to 2000 S/cm, and an opticaltransmittance at 550 nm of greater than or equal to 90%, more typicallygreater than or equal to 93%, even more typically greater than or equalto 95% and still more typically of greater than or equal to 98%.

In one embodiment, the aqueous gel of the present invention comprises,based on 100 pbw of the gel,

(A) from about 2 pbw to about 90 pbw of a polymer network, based on 100pbw of the polymer network:

-   -   (i) from about 10 to about 40 pbw, more typically from about 15        to about 35 pbw, and even more typically from about 20 to about        35 pbw of an electrically conductive polymer comprising a        mixture of, based on 100 pbw of the mixture:        -   (1) from about 20 to about 50 pbw of            poly(3,4-ethylenedioxythiophene), and        -   (2) from about 50 to about 80 pbw of poly(styrene sulfonic            acid) dopant, and    -   (ii) from about 60 to about 90 pbw, more typically from about 65        to about 85 pbw, and even more typically from about 65 to about        80 pbw of an ionic liquid comprising        1-ethyl-3-methyl-imidazolium tetracyanoborate,        (B) from about 10 pbw to about 98 pbw of an aqueous liquid        medium, wherein the ratio of the total amount by weight of the        ionic liquid in such film to the total amount by weight of the        electrically conductive polymer in such film is typically from        about 1.5:1 to about 45:1, more typically from 1.7:1 to 20:1,        even more typically from about 1.7:1 to about 10:1, and still        more typically from 2:1 to 8:1.

In one embodiment, the polymer foam of the present invention and polymerfoam component of the electronic device of the present invention eachcomprise the product obtained by contacting, based on 100 pbw of thepolymer foam:

-   -   (i) from about 10 to about 40 pbw, more typically from about 15        to about 35 pbw, and even more typically from about 20 to about        35 pbw of an electrically conductive polymer comprising a        mixture of, based on 100 pbw of the mixture:        -   (1) from about 20 to about 50 pbw of            poly(3,4-ethylenedioxythiophene), and        -   (2) from about 50 to about 80 pbw of poly(styrene sulfonic            acid) dopant, and    -   (ii) from about 60 to about 90 pbw, more typically from about 65        to about 85 pbw, and even more typically from about 65 to about        80 pbw of an ionic liquid comprising        1-ethyl-3-methyl-imidazolium tetracyanoborate,        wherein the ratio of the total amount by weight of the ionic        liquid in such film to the total amount by weight of the        electrically conductive polymer in such film is typically from        about 1.5:1 to about 45:1, more typically from 1.7:1 to 20:1,        even more typically from about 1.7:1 to about 10:1, and still        more typically from 2:1 to 8:1.

In one embodiment, the respective polymer gel of the present inventionand polymer gel component of the electronic device of the presentinvention each exhibit a sheet resistance of less than or equal to50Ω/□, more typically, of less than or equal to 10Ω/□.

In one embodiment, polymer film according to the present invention isused as an electrode layer, more typically, an anode layer, of anelectronic device.

In one embodiment, the polymer film according to the present inventionis used as a buffer layer of an electronic device.

In one embodiment, a polymer film according to the present invention isused as a combined electrode and buffer layer, typically a combinedanode and buffer layer, of an electronic device.

In one embodiment, the electronic device of the present invention is anelectronic device 100, as shown in FIG. 1, having an anode layer 101, anelectroactive layer 104, and a cathode layer 106 and optionally furtherhaving a buffer layer 102, hole transport layer 103, and/or electroninjection/transport layer or confinement layer 105, wherein at least oneof the layers of the device is a polymer film according to the presentinvention. The device 100 may further include a support or substrate(not shown), that can be adjacent to the anode layer 101 or the cathodelayer 106. more typically, adjacent to the anode layer 101. The supportcan be flexible or rigid, organic or inorganic. Suitable supportmaterials include, for example, glass, ceramic, metal, and plasticfilms.

In one embodiment, anode layer 101 of device 100 comprises a polymerfilm according to the present invention. The polymer film of the presentinvention is particularly suitable as anode layer 106 of device 100because of its high electrical conductivity.

In one embodiment, anode layer 101 itself has a multilayer structure andcomprises a layer of the polymer film according to the presentinvention, typically as the top layer of the multilayer anode, and oneor more additional layers, each comprising a metal, mixed metal, alloy,metal oxide, or mixed oxide. Suitable materials include the mixed oxidesof the Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11elements, the elements in Groups 4, 5, and 6, and the Group 8-10transition elements. If the anode layer 101 is to be light transmitting,mixed oxides of Groups 12, 13 and 14 elements, such as indium-tin-oxide,may be used. As used herein, the phrase “mixed oxide” refers to oxideshaving two or more different cations selected from the Group 2 elementsor the Groups 12, 13, or 14 elements. Some non-limiting, specificexamples of materials for anode layer 101 include, but are not limitedto, indium-tin-oxide, indium-zinc-oxide, aluminum-tin-oxide, gold,silver, copper, and nickel. The mixed oxide layer may be formed by achemical or physical vapor deposition process or spin-cast process.Chemical vapor deposition may be performed as a plasma-enhanced chemicalvapor deposition (“PECVD”) or metal organic chemical vapor deposition(“MOCVD”). Physical vapor deposition can include all forms ofsputtering, including ion beam sputtering, as well as e-beam evaporationand resistance evaporation. Specific forms of physical vapor depositioninclude radio frequency magnetron sputtering and inductively-coupledplasma physical vapor deposition (“IMP-PVD”). These depositiontechniques are well known within the semiconductor fabrication arts.

In one embodiment, the mixed oxide layer is patterned. The pattern mayvary as desired. The layers can be formed in a pattern by, for example,positioning a patterned mask or resist on the first flexible compositebarrier structure prior to applying the first electrical contact layermaterial. Alternatively, the layers can be applied as an overall layer(also called blanket deposit) and subsequently patterned using, forexample, a patterned resist layer and wet chemical or dry etchingtechniques. Other processes for patterning that are well known in theart can also be used.

In one embodiment, device 100 comprises a buffer layer 102 and thebuffer layer 102 comprises a polymer film according to the presentinvention.

In one embodiment, a separate buffer layer 102 is absent and anode layer101 functions as a combined anode and buffer layer. In one embodiment,the combined anode/buffer layer 101 comprises a polymer film accordingto the present invention.

In some embodiments, optional hole transport layer 103 is present,either between anode layer 101 and electroactive layer 104, or, in thoseembodiments that comprise buffer layer 102, between buffer layer 102 andelectroactive layer 104. Hole transport layer 103 may comprise one ormore hole transporting molecules and/or polymers. Commonly used holetransporting molecules include, but are not limited to:4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine,4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,1,1-bis((di-4-tolylamino)phenyl)cyclohexane,N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-(1,1′-(3,3′-dimethyl)biphenyl)-4,4′-diamine,tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine,.alpha-phenyl-4-N,N-diphenylaminostyrene, p-(diethylamino)benzaldehydediphenylhydrazone, triphenylamine,bis(4-(N,N-diethylamino)-2-methylphenyl)(4-methylphenyl)methane,1-phenyl-3-(p-(diethylamino)styryl)-5-(p-(diethylamino)phenyl)pyrazoline,1,2-trans-bis(9H-carbazol-9-yl)cyclobutane,N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine, and porphyriniccompounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules, such asthose mentioned above, into polymers such as polystyrene andpolycarbonate.

The composition of electroactive layer 104 depends on the intendedfunction of device 100, for example, electroactive layer 104 can be alight-emitting layer that is activated by an applied voltage (such as ina light-emitting diode or light-emitting electrochemical cell), or alayer of material that responds to radiant energy and generates a signalwith or without an applied bias voltage (such as in a photodetector). Inone embodiment, electroactive layer 104 comprises an organicelectroluminescent (“EL”) material, such as, for example,electroluminescent small molecule organic compounds, electroluminescentmetal complexes, and electroluminescent conjugated polymers, as well asmixtures thereof. Suitable EL small molecule organic compounds include,for example, pyrene, perylene, rubrene, and coumarin, as well asderivatives thereof and mixtures thereof. Suitable EL metal complexesinclude, for example, metal chelated oxinoid compounds, such astris(8-hydroxyquinolate)aluminum, cyclo-metallated iridium and platinumelectroluminescent compounds, such as complexes of iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., U.S. Pat. No. 6,670,645, and organometalliccomplexes such as those described in, for example, Published PCTApplications WO 03/008424, as well as mixtures any of such EL metalcomplexes. Examples of EL conjugated polymers include, but are notlimited to poly(phenylenevinylenes), polyfluorenes,poly(spirobifluorenes), polythiophenes, and poly(p-phenylenes), as wellas copolymers thereof and mixtures thereof.

Optional layer 105 can function as an electron injection/transport layerand/or a confinement layer. More specifically, layer 105 may promoteelectron mobility and reduce the likelihood of a quenching reaction iflayers 104 and 106 would otherwise be in direct contact. Examples ofmaterials suitable for optional layer 105 include, for example, metalchelated oxinoid compounds, such asbis(2-methyl-8-quinolinolato)(para-phenyl-phenolato)aluminum(III) andtris(8-hydroxyquinolato)aluminum,tetrakis(8-hydroxyquinolinato)zirconium, azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole,3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole, and1,3,5-tri(phenyl-2-benzimidazole)benzene, quinoxaline derivatives suchas 2,3-bis(4-fluorophenyl)quinoxaline, phenanthroline derivatives suchas 9,10-diphenylphenanthroline and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and as well as mixturesthereof. Alternatively, optional layer 105 may comprise an inorganicmaterial, such as, for example, BaO, LiF, Li₂O.

Cathode layer 106 can be any metal or nonmetal having a lower workfunction than anode layer 101. In one embodiment, anode layer 101 has awork function of greater than or equal to about 4.4 eV and cathode layer106 has a work function less than about 4.4 eV. Materials suitable foruse as cathode layer 106 are known in the art and include, for example,alkali metals of Group 1, such as Li, Na, K, Rb, and Cs, Group 2 metals,such as, Mg, Ca, Ba, Group 12 metals, lanthanides such as Ce, Sm, andEu, and actinides, as well as aluminum, indium, yttrium, andcombinations of any such materials. Specific non-limiting examples ofmaterials suitable for cathode layer 106 include, but are not limitedto, Barium, Lithium, Cerium, Cesium, Europium, Rubidium, Yttrium,Magnesium, Samarium, and alloys and combinations thereof. Cathode layer106 is typically formed by a chemical or physical vapor depositionprocess. In some embodiments, the cathode layer will be patterned, asdiscussed above in reference to the anode layer 101.

In one embodiment, an encapsulation layer (not shown) is deposited overcathode layer 106 to prevent entry of undesirable components, such aswater and oxygen, into device 100. Such components can have adeleterious effect on electroactive layer 104. In one embodiment, theencapsulation layer is a barrier layer or film. In one embodiment, theencapsulation layer is a glass lid.

Though not shown in FIG. 1, it is understood that device 100 maycomprise additional layers. Other layers that are known in the art orotherwise may be used. In addition, any of the above-described layersmay comprise two or more sub-layers or may form a laminar structure.Alternatively, some or all of anode layer 101, buffer layer 102, holetransport layer 103, electron transport layer 105, cathode layer 106,and any additional layers may be treated, especially surface treated, toincrease charge carrier transport efficiency or other physicalproperties of the devices. The choice of materials for each of thecomponent layers is preferably determined by balancing the goals ofproviding a device with high device efficiency with device operationallifetime considerations, fabrication time and complexity factors andother considerations appreciated by persons skilled in the art. It willbe appreciated that determining optimal components, componentconfigurations, and compositional identities would be routine to thoseof ordinary skill of in the art.

The various layers of the electronic device can be formed by anyconventional deposition technique, including vapor deposition, liquiddeposition (continuous and discontinuous techniques), and thermaltransfer. Continuous deposition techniques, include but are not limitedto, spin coating, gravure coating, curtain coating, dip coating,slot-die coating, spray coating, and continuous nozzle coating.Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing. Other layers in thedevice can be made of any materials which are known to be useful in suchlayers upon consideration of the function to be served by such layers.

In one embodiment of the device 100, the different layers have thefollowing range of thicknesses:

anode layer 101, typically 500-5000 Angstroms (“Å”), more typically,1000-2000 Å,

optional buffer layer 102: typically 50-2000 Å, more typically, 200-1000Å,

optional hole transport layer 103: typically 50-2000 Å, more typically,100-1000 Å,

photoactive layer 104: typically, 10-2000 Å, more typically, 100-1000 Å,

optional electron transport layer: typically 105, 50-2000 Å, moretypically, 100-1000 Å, and

cathode layer 106: typically 200-10000 Å, more typically, 300-5000 Å.

As is known in the art, the location of the electron-hole recombinationzone in the device, and thus the emission spectrum of the device, can beaffected by the relative thickness of each layer. The appropriate ratioof layer thicknesses will depend on the exact nature of the device andthe materials used.

In one embodiment, the electronic device of the present invention,comprises:

-   (a) an anode or combined anode and buffer layer 101,-   (b) a cathode layer 106,-   (c) an electroactive layer 104, disposed between anode layer 101 and    cathode layer 106,-   (d) optionally, a buffer layer 102, typically disposed between anode    layer 101 and electroactive layer 104,-   (e) optionally, a hole transport layer 105, typically disposed    between anode layer 101 and electroactive layer 104, or if buffer    layer 102 is present, between buffer layer 102 and electroactive    layer 104, and-   (f) optionally an electron injection layer 105, typically disposed    between electroactive layer 104 and cathode layer 106,    wherein at least one of the layers of the device, typically at least    one of the anode or combined anode and buffer layer 101 and, if    present, buffer layer 102, comprises a polymer film according to the    present invention.

The electronic device of the present invention may be any device thatcomprises one or more layers of semiconductor materials and makes use ofthe controlled motion of electrons through such one or more layers, suchas, for example:

a device that converts electrical energy into radiation, such as, forexample, a light-emitting diode, light emitting diode display, diodelaser, a liquid crystal display, or lighting panel,

a device that detects signals through electronic processes, such as, forexample, a photodetector, photoconductive cell, photoresistor,photoswitch, phototransistor, phototube, infrared (“IR”) detector,biosensor, or a touch screen display device,

a device that converts radiation into electrical energy, such as, forexample, a photovoltaic device or solar cell, and

a device that includes one or more electronic components with one ormore semiconductor layers, such as, for example, a transistor or diode.

In one embodiment, the electronic device of the present invention is adevice for converting electrical energy into radiation, and comprises ananode 101 that comprises a polymer film according to the presentinvention, a cathode layer 106, an electroactive layer 104 that iscapable of converting electrical energy into radiation, disposed betweenthe anode layer 101 layer and the cathode layer 106, and optionallyfurther comprising a buffer layer 102, a hole transport layer 103,and/or an electron injection layer 105. In one embodiment, the device isa light emitting diode (“LED”) device and the electroactive layer 104 ofthe device is an electroluminescent material, even more typically, andthe device is an organic light emitting diode (“OLED”) device and theelectroactive layer 104 of the device is organic electroluminescentmaterial. In one embodiment, the OLED device is an “active matrix” OLEDdisplay, wherein, individual deposits of photoactive organic films maybe independently excited by the passage of current, leading toindividual pixels of light emission. In another embodiment, the OLED isa “passive matrix” OLED display, wherein deposits of photoactive organicfilms may be excited by rows and columns of electrical contact layers.

In one embodiment, the electronic device of the present invention is adevice for converting radiation into electrical energy, and comprises ananode 101 that comprises a polymer film according to the presentinvention, a cathode layer 106, an electroactive layer 104 comprising amaterial that is capable of converting radiation into electrical energy,disposed between the anode layer 101 layer and the cathode layer 106,and optionally further comprising a buffer layer 102, a hole transportlayer 103, and/or an electron injection layer 105.

In operation of one embodiment of device 100, such as a device forconverting electrical energy into radiation, a voltage from anappropriate power supply (not depicted) is applied to device 100 so thatan electrical current passes across the layers of the device 100 andelectrons enter electroactive layer 104, and are converted intoradiation, such as in the case of an electroluminescent device, arelease of photon from electroactive layer 104.

In operation of another embodiment of device 100, such as device forconverting radiation into electrical energy, device 100 is exposed toradiation impinges on electroactive layer 104, and is converted into aflow of electrical current across the layers of the device.

In one embodiment, the electronic device 100 is a battery comprising ananode 101, a cathode layer 106 and an electrolyte layer 104 disposedbetween the anode layer and cathode layer, wherein the electrolyte layer104 comprises a polymer film according to the present invention, in theform of an aqueous gel.

In one embodiment, the electronic device 100 comprises an electroactivelayer 104, wherein the electroactive layer 104 comprises a polymer foamaccording to the present invention.

Examples 1-13 and Comparative Examples C1-C26

The compositions of Examples 1-4 and Comparative Examples C1-C20 weremade by mixing the components listed below:

PEDOT:PSS 1 Aqueous dispersion containing 1.3 percent by weight (“wt %”)of poly(3,4- ethylenedioxythiophene:poly(styrene sulfonic acid) blend(Low Conductive (Sigma Aldrich)) PEDOT:PSS 2 Aqueous dispersioncontaining 1.3 wt % of poly(3,4- ethylenedioxythiophene: poly(styrenesulfonic acid) blend (Clevios PH 750 (H. C. Starck)) PEDOT:PSS 3 Aqueousdispersion containing 1.3 wt % of poly(3,4- ethylenedioxythiophene:poly(styrene sulfonic acid) blend (Clevios PH 1000 (H.C. Starck)) DMSODimethyl sulfoxide (Sigma Aldrich) EG Ethylene glycol (VWR) DMF Dimethylformamide (Sigma Aldrich) IL 1 1-ethyl-3-methylimidazoliumtetracyanoborate (Merck)in the relative amounts set forth in TABLES I-III below. Thecompositions were each spin-coated on plastic substrates (100 microLiter(“μL”) aliquot of the respective composition on a 1.5×1.5 centimeter(“cm”) at 380 revolutions per minute (“rpm”) for 18 seconds and then at3990 rpm for 1 minute) to form a film of the composition. Twospin-coated samples were each dried in the oven for 1 hour and were theneach dried at room temperature.

The resistance of each of the spin-coated films was measured between twoelectrodes of silver paste on opposite sides of a theoretical square,using a multimeter. The optical transmittance of the spin-coated filmswere characterized with a Cary 100 Bio UV-Visible spectrophotometer. Thesheet resistance, in units of Ohms per square (“Ω/□”), and transmittancein the range of 300-800 nm, in units of percent transmittance (%), foreach sample are set forth in TABLES IA, IB, IIA, IIB, IIIA, IIIB, and IVbelow.

TABLE IA Example # 1 2 3 4 5 6 7 PEDOT:PSS 1 99.58 99.06 97.89 97.3797.03 — — PEDOT:PSS 2 — — — — — 99.49 98.79 PEDOT:PSS 3 — — — — — — — IL1 0.42 0.94 2.11 2.63 2.97 0.51 1.21 Resistance (Ω/□) 329000 9350 1130435 434 108000 262 Transmittance >98 >98 >98 >98 >98 >98 >98 (%)

TABLE IB Example # 8 9 10 11 12 13 PEDOT:PSS 1 — — — — — — PEDOT:PSS 297.91 97.44 96.82 — — — PEDOT:PSS 3 — — — 99 98 97.34 IL 1 2.09 2.563.18 1 2 2.66 Resistance 135 175 77 108 84 52 (Ω/□))Transmittance >98 >98 >98 >98 >98 >98 (%)

TABLE IIA Comparative Example # C1 C2 C3 C4 C5 C6 C7 PEDOT:PSS 1 10098.60 99.05 99 94.66 94.86 95.39 DMSO — 1.40 — — 5.34 — — EG — — 0.95 —— 5.14 — DMF — — — 1 — — 4.61 Resistance 1480000 88500 343000 4280001140 2070 5320 (Ω/□) Transmittance >98 >98 >98 >98 >98 >98 >98 (%)

TABLE IIB Comparative Example # C8 C9 C10 C11 C12 C13 PEDOT:PSS 1 89.5789.63 90.11 78.3 80.56 80.08 DMSO 10.43 — — 21.7 — — EG — 10.37 — —19.44 — DMF — — 9.89 — — 19.92 Resistance 890 1550 1140 1000 798 1340(Ω/□) Transmittance >98 >98 >98 >98 >98 >98 (%)

TABLE IIIA Comparative Example # C14 C15 C16 C17 C18 C19 C20 PEDOT:PSS 2100 98.75 98.82 98.83 95.12 92.85 94.9 DMSO — 1.25 — — 4.88 — — EG — —1.18 — — 7.15 — DMF — — — 1.17 — — 5.10 Resistance 545000 39000 178000135000 566 295 996 (Ω/□) Transmittance >98 >98 >98 >98 >98 >98 >98 (%)

TABLE IIIB Comparative Example # C21 C22 C23 C24 C25 C26 PEDOT:PSS 290.02 89.89 90.04 80.28 80.09 80.16 DMSO 9.98 — — 19.72 — — EG — 10.11 —— 19.91 — DMF — — 9.96 — — 19.84 Resistance 307 372 393 284 243 316(Ω/□) Transmittance >98 >98 >98 >98 >98 >98 (%)

TABLE IV Comparative Example # C27 C28 C29 C30 PEDOT:PSS 3 100 98.8795.16 89.98 DMSO — 1.13 4.84 10.02 Resistance 315000 21200 199 168 (Ω/□)Transmittance >98 >98 >98 >98 (%)

Examples 14-24 and Comparative Example C31

The compositions of Examples 14 to 24 and Comparative Example C31 weremade as follows. In each case, ionic liquid (ethyl-3-methylimidazoliumtetracyanoborate (melting point 13° C., EMD Chemicals) was added, in therespective amount set forth below in TABLE V, to 1 gram of a 1.3 wt %aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C. Starck) and mixed.

The viscosity of the dispersions increased with increasing the amount ofionic liquid. At a ratio of 1.7 pbw ionic liquid per 1 pbw PEDOT:PSSpolymer solids, the composition began to show evidence of gelation and acomplete gel was formed at a ratio of 2 pbw ionic liquid per 1 pbwPEDOT:PSS polymer solids. Gels were formed up to a ratio of about 45 pbwionic liquid per 1 pbw PEDOT:PSS polymer solids. Compositions comprisinga ratio of greater than about 45 pbw ionic liquid per 1 pbw PEDOT:PSSpolymer solids formed conductive pastes.

A 100 microliter aliquot of each of the respective liquid compositionsof Examples 14, 15, 16, and 17 and Comparative Example C31 was spincoated on a plastic sheet at 380 revolutions per minutes (“rpm”) for 18seconds and then 3990 rpm for 1 minute to form a film. The spin coatedfilms were dried in the oven at 120° C. for 20 minutes each and thenstored at room temperature.

Each of the gels obtained in the compositions of Examples 18 to 24 wasfreeze dried. Porous compressible foam structures, having a roughlyright circular cylindrical shape of roughly 1.5 mm in diameter and from0.4 to 3.5 mm in height, were obtained. The foams were not soluble inwater when subjected to (i) mechanical stirring for more than one day,(ii) sonication for more than one hour, or (iii) heating up to 60° C.The foams were flexible and deformable under low compressive force, forexample, finger pressure, and recovered their initial shape after thecompressive force was removed.

The resistance of each spin coated film was measured between twoelectrodes of silver paste on opposite sides of a theoretical square,using a millimeter. The sheet resistance values (in Ohms per square(“Ω/□”)) exhibited by each the films of Examples 14-17 and ComparativeExample 31 are set forth in TABLES VA and VB below. The resistance ofeach of the foams of Examples 18 to 24, was measured directly bycompressing the foam and using a multimeter, and in each case was foundto be in the range of about 50 to about 100Ω, depending on the thicknessof the compressed foam.

TABLE VA Example # C31 14 15 16 17 18 Amount ionic liquid (g) 0 0.00540.01 0.176 0.02 0.022 per 0.013 g PEDOT:PSS polymer Ratio (wt:wt) ofionic No ionic 0.42 0.77 1.31 1.54 1.69 liquid to PEDOT:PSS liquidpolymer Physical State liquid liquid liquid liquid Liquid gel Resistance(Ω/□) 300,000 2,000 100 60 35 —

TABLE VB Example # 19 20 21 22 23 24 Amount ionic liquid (g) 0.02980.0358 0.1 0.16 0.21 0.52 per 0.013 g PEDOT:PSS polymer Ratio (wt:wt) ofionic 2.28 2.75 7.69 12.41 15.87 40.16 liquid to PEDOT:PSS polymerPhysical State gel gel gel gel gel gel Resistance (Ω/□) — — — — — —

Examples 25-34

The compositions of Examples 25 to 29 were made by adding an ionicliquid (1-Ethyl-3-methylimidazolium dicyanamide (“EMIM N(CN)2”)), in therespective amounts set forth below in TABLE VI, to 1 gram of a 1.3 wt %aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C. Starck) andmixing.

The compositions of Examples 30-34 were made by adding an ionic liquid(1-Ethyl-3-methylimidazolium hexafluorophosphate (“EMIM PF6”)), in therespective amounts set forth below in TABLE VII, to 1 gram of a 1.3 wt %aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C. Starck) andmixing.

A 100 microliter aliquot of each of the respective liquid compositionsof Examples 25 to 34 was spin coated on a plastic sheet at 380revolutions per minutes (“rpm”) for 18 seconds and then 3990 rpm for 1minute to form a film. The spin coated films were dried in the oven at120° C. for 20 minutes each and then stored at room temperature. Theresistance of each spin coated film was measured between two electrodesof silver paste on opposite sides of a theoretical square, using amillimeter. The amount ionic liquid (expressed as grams (“g”) ionicliquid per 0.013 g PEDOT:PSS polymer) in each aqueous polymer/ionicliquid dispersion, the ratio (wt:wt) of ionic liquid to PEDOT:PSSpolymer in the aqueous polymer/ionic liquid dispersion and film, thephysical state of the aqueous polymer/ionic liquid dispersion, and thesheet resistance of the film (in Ohms per square (“Ω/□”)), for each ofExamples 25 to 34 are set forth in the respective TABLES VI and VIIbelow.

TABLE VI Example # EMIM N(CN)2 25 26 27 28 29 Amount ionic liquid (g)0.00620 0.0087 0.0105 0.0116 0.0145 per 0.013 g PEDOT:PSS polymer Ratio(wt:wt) of ionic 0.477 0.669 0.808 0.892 1.115 liquid to PEDOT:PSSpolymer Physical state liquid liquid liquid liquid liquid Resistance(Ω/□)) 155900 45700 10380 650 418

TABLE VII Ionic liquid = Example # EMIM PF6 30 31 32 33 34 Amount ionic0.0060 0.0089 0.0258 0.0240 0.0401 liquid (g) per 0.013 g PEDOT:PSSpolymer Ratio (wt:wt) of ionic 0.462 0.685 1.985 1.846 3.085 liquid toPEDOT:PSS polymer Physical state liquid liquid liquid liquid liquidResistance (Ω/□) 1260000 193800 2680 239 244

Examples 35 to 43 and Comparative Examples C32 to C36

The compositions of Examples 35 to 38 were made by adding an ionicliquid (1-Ethyl-3-methylimidazolium tetracyanoborate (“EMIM TCB”)), inthe respective amounts set forth below in TABLE VIII, to 1 gram of a 1.3wt % aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C. Starck),without stirring the dispersion during the addition and then stirring(Process 1 “P1”)).

The compositions of Examples 39 to 43 were made by adding an ionicliquid (1-Ethyl-3-methylimidazolium tetracyanoborate (“EMIM TCB”)), inthe respective amounts set forth below in TABLE IX, to 1 gram of a 1.3wt % aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C. Starck) whilestirring the dispersion, with continued stirring (Process 2 “P2”)).

The compositions of Comparative Examples C32 to C36 were made by addingan ionic liquid (1-Ethyl-3-methylimidazolium tetrafluoroborate (“EMIMBF4”)), in the respective amount set forth below in TABLE X, to 1 gramof a 1.3 wt % aqueous dispersion of PEDOT:PSS (Clevios PH 1000 H.C.Starck) while stirring the dispersion, with continued stirring (Process2 “P2”)).

A 100 microliter aliquot of each of the respective liquid compositionsof Examples 35 to 43 and Comparative Examples C32 to C36 was spin coatedon a glass sheet at 380 revolutions per minutes (“rpm”) for 18 secondsand then 3990 rpm for 1 minute to form a film. The spin coated filmswere dried in the oven at 120° C. for 20 minutes each and then stored atroom temperature. The resistance of each spin coated film was measuredbetween two electrodes of silver paste on opposite sides of atheoretical square, using a millimeter. The thickness of each film wasmeasured using an alpha-SE™ spectroscopic ellipsometer (J. A. Wollam &Co., Inc.). The conductivity of each film was calculated according toformula (I), as described above.

The amount ionic liquid (expressed as grams (“g”) ionic liquid per 0.013g PEDOT:PSS polymer) in each aqueous polymer/ionic liquid dispersion,the ratio (wt:wt) of ionic liquid to PEDOT:PSS polymer in the aqueouspolymer/ionic liquid dispersion and film, the physical state of theaqueous polymer/ionic liquid dispersion, the resistance (in ohm/sq) ofthe film, sheet resistance values (in Ohms per square (“Ω/□”)) theamount of ionic liquid in film (as percent by weigh (“wt %”) of thefilm), the thickness of the film (in nanometers (“nm”)), and theconductivity (in Siemens per centimeter (“S/cm”)) for each of Examples35 to 43 and Comparative Examples C32 to C36 are set forth in therespective TABLES VIII, IX, and X below.

TABLE VIII EMIM TCB, Example # added directly 35 36 37 38 Amount ionic 00.00600 0.0094 0.0159 liquid (g) per 0.013 g PEDOT:PSS polymer Ratio(wt:wt) of ionic 0 0.462 0.723 1.223 liquid to PEDOT:PSS polymerPhysical state liquid liquid liquid liquid Resistance (Ω/□) 235000 237148 50 wt % EMIM TCB in film 0 31 42 55 Thickness (nm) 61 61 74 96Conductivity (S/cm) 0.68 811 933 2083

TABLE IX EMIM TCB, added Example # while stirring 39 40 41 42 43 Amount0 0.00470 0.0079 0.0127 0.0167 ionic liquid (g) per 0.013 g PEDOT:PSSpolymer Ratio (wt:wt) 0 0.362 0.608 0.977 1.285 of ionic liquid toPEDOT:PSS polymer Physical liquid liquid liquid liquid liquid stateResistance 235000 184 99 86 69 (Ω/□) wt % EMIM 0 27 37 50 56 TCB in filmThickness 61 78 107 194 235 (nm) Conductivity 0.68 699 941 596 621(S/cm)

TABLE X BMIM BF4, added Example # while stirring C32 C33 C34 C36 Amountionic liquid 0 0.0064 0.0092 0.0133 (g) per 0.013 g PEDOT:PSS polymerRatio (wt:wt) of ionic 0 0.49 0.71 1.02 liquid to PEDOT:PSS polymer (%)Physical state liquid liquid liquid liquid Resistance (Ω/□) 235000351100 2650 110 wt % EMIM TCB 0 32 41 50 in film Thickness (nm) 61 115200 317 Conductivity (S/cm) 0.68 0.25 19 287

The conductivity of the PEDT:PSS/EMIM TCB films of Examples 39 to 43(“PEDOT PSS EMIM TCB P2”) was greater than the conductivity of theanalogous PEDOT:PSS/EMIM TCB films of Examples 35 to 38 (“PEDOT PSS EMIMTCB P1”), as shown graphically in FIG. 2.

the conductivity of the PEDT:PSS/EMIM TCB films of Examples 39 to 43(“PEDOT PSS EMIM TCB P2”) was significantly greater than theconductivity of the analogous PEDOT:PSS/EMIM BF4 films of ComparativeExamples C32 to C36 ((“PEDOT PSS EMIM BF4 P2”), as shown graphically inFIG. 2.

What is claimed is:
 1. A polymer gel, comprising: (a) a polymer network,comprising: (i) an electrically conductive polymer, comprising: (1) oneor more electrically conductive polythiophene polymers, and (2) one ormore water soluble polymeric acid dopants, wherein the one or moreelectrically conductive polythiophene polymers comprisepoly(3,4-ethylenedioxythiophene) and one or more water soluble polymericacid dopants comprise a poly(styrene sulfonic acid) dopant and (ii) anamount of an ionic liquid effective to gel the electrically conductivepolymer, wherein the ionic liquid comprises 1-ethyl-3-methyl-imidazoliumtetracyanoborate, wherein the ratio of the total amount by weight of theionic liquid to the total amount by weight of the electricallyconductive polymer is from about 1.7:1 to about 45:1, and (b) a liquidmedium supported within the polymer network.
 2. The polymer gel of claim1, wherein the gel comprises, based on 100 parts by weight of thepolymer gel, (a) from about 2 parts by weight to about 90 parts byweight of the polymer network, wherein the polymer network comprises,based on 100 parts by weight of the network: (i) from about 10 parts byweight to about 40 parts by weight, of the electrically conductivepolymer, and (ii) from about 60 parts by weight to about 90 parts byweight, of the ionic liquid, and (b) from about 10 parts by weight toabout 98 parts by weight of the liquid medium.
 3. An electronic device,comprising a plurality of layers, wherein at least one layer of theplurality of layers comprises a polymer gel according to claim
 1. 4. Anelectronic device 100 according to claim 3, wherein the devicecomprises: (a) an anode or combined anode and buffer layer 101, (b) acathode layer 106, (c) an electroactive layer 104, disposed betweenanode layer 101 and cathode layer 106, (d) optionally, a buffer layer102, disposed between anode layer 101 and electroactive layer 104, (e)optionally, a hole transport layer 105, disposed between anode layer 101and electroactive layer 104, or if buffer layer 102 is present, betweenbuffer layer 102 and electroactive layer 104, and (f) optionally anelectron injection layer 105, disposed between electroactive layer 104and cathode layer
 106. 5. An electronic device 100 according to claim 4,wherein the device is a battery comprising an anode 101, a cathode layer106 and an electrolyte layer 104 disposed between the anode layer andcathode layer, and the electrolyte layer 104 comprises the polymer gel.